CN101277912B - Porous carbon sheet and process for production thereof - Google Patents
Porous carbon sheet and process for production thereof Download PDFInfo
- Publication number
- CN101277912B CN101277912B CN2006800359501A CN200680035950A CN101277912B CN 101277912 B CN101277912 B CN 101277912B CN 2006800359501 A CN2006800359501 A CN 2006800359501A CN 200680035950 A CN200680035950 A CN 200680035950A CN 101277912 B CN101277912 B CN 101277912B
- Authority
- CN
- China
- Prior art keywords
- sheet
- mentioned
- porous carbon
- precursor fiber
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 448
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 443
- 238000000034 method Methods 0.000 title claims description 372
- 230000008569 process Effects 0.000 title claims description 151
- 238000004519 manufacturing process Methods 0.000 title claims description 104
- 239000000835 fiber Substances 0.000 claims abstract description 430
- 239000002243 precursor Substances 0.000 claims abstract description 240
- 239000011347 resin Substances 0.000 claims abstract description 210
- 229920005989 resin Polymers 0.000 claims abstract description 209
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 112
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims description 129
- 238000005452 bending Methods 0.000 claims description 95
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000003856 thermoforming Methods 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 description 95
- 229920000049 Carbon (fiber) Polymers 0.000 description 93
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 93
- 230000006835 compression Effects 0.000 description 32
- 238000007906 compression Methods 0.000 description 32
- 239000007789 gas Substances 0.000 description 27
- 239000000446 fuel Substances 0.000 description 24
- 229920003987 resole Polymers 0.000 description 24
- 239000000463 material Substances 0.000 description 19
- 238000007669 thermal treatment Methods 0.000 description 19
- 238000009423 ventilation Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010586 diagram Methods 0.000 description 13
- 238000010304 firing Methods 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229920002239 polyacrylonitrile Polymers 0.000 description 8
- 239000005518 polymer electrolyte Substances 0.000 description 8
- 208000037656 Respiratory Sounds Diseases 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000008676 import Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000010409 ironing Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 238000001149 thermolysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 229920002955 Art silk Polymers 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
- C04B38/0032—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors one of the precursor materials being a monolithic element having approximately the same dimensions as the final article, e.g. a paper sheet which after carbonisation will react with silicon to form a porous silicon carbide porous body
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Paper (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a porous carbon sheet obtained by binding separate carbon short fibers with a carbonization product of a resin, wherein the pore mode diameter of the sheet is 45 to 90[mu]m and the mean fiber diameter of the carbon short fibers is 5 to 20[mu]m. The sheet can be produced by thermoforming a precursor fiber sheet comprising carbon short fibers of 15 to 30g/m2 in basis weight and a thermosetting resin of 30 to 80g/m2 in basis weight by hot plates having a certain clearance and carbonizing the thermosetting resin contained in the thermoformed precursor fiber sheet.
Description
Technical field
The present invention relates to porous carbon sheet.Porous carbon sheet of the present invention contains carbon chopped fiber and resin carbonation thing, and carbon chopped fiber is bonding by the resin carbonation thing.In addition, the invention still further relates to the manufacture method of porous carbon sheet.
Porous carbon sheet of the present invention has the needed multifrequency nature of carbon paper as the gas diffuser of fuel cell simultaneously.Do not satisfy simultaneously the porous carbon sheet of these multifrequency natures in the past.Specifically, porous carbon sheet of the present invention satisfies simultaneously all that ventilation property is high, electroconductibility is high, the residual set amount (residual deformation) after the compression is little.
Porous carbon sheet of the present invention is preferably used as the gas diffuser material that automobile is used polymer electrolyte fuel cell.
Background technology
Polymer electrolyte fuel cell is to generate electricity by supply hydrogen and oxygen, generates water by electric power generation reaction.The gas diffuser material that consists of the film-electrode bond of fuel cell generation electric power generation reaction adopts carbon fiber usually with the bonding carbon paper that forms of resin carbonation thing.Requiring in the purposes of high output density at automobile etc., is at the high regional operating fuel cell of current density, so the amount of the water that produces of unit reaction area also increases.In this case, it is emphasis that the generation water that how efficiently will react is discharged, as the demanding ventilation property of carbon paper of fuel cell gas diffuser material.
For above-mentioned problem, be by suitable pressure the precursor fiber sheet that contains the amount minimizing that is immersed in the thermosetting resin in the carbon fiber paper to be carried out heating and pressurizing to process in the patent documentation 1.Can in the density that keeps carbon fiber, reduce by this method the amount of bonding carbon, make the carbon paper low density, the ventilation property of thickness direction is improved.But, if reduce the amount of bonding carbon, the then bonding minimizing of counting of carbon fiber and resin carbonation thing, the problem that therefore has the ratio resistance of carbon paper thickness direction to increase.Therefore in the patent documentation 1 described carbon paper, there is the relation of accepting or rejecting selection in the ventilation property of thickness direction with the ratio resistance of thickness direction, is difficult to fully satisfy both.
Be the precursor fiber sheet of impregnation graphite granule and thermosetting resin in the low carbon fiber paper of weight per unit area not to be carried out heating and pressurizing to process in the patent documentation 2, only carry out heat treated.The carbon paper carbon fiber density that is obtained by this manufacture method reduces, but therefore the high graphite granule density rising of electroconductibility can realize low-resistivity and high air permeability by face simultaneously.But carbon fiber density contained in the physical strength of carbon paper and the carbon paper has very large dependency, so there is the rear large problem of residual set amount (residual deformation amount) of through-thickness compression in patent documentation 2 described carbon papers.
The large carbon paper of residual set amount is stacked into fuel cell after the compression of used thickness direction, then carbon paper can fall into the groove of being located on the barrier film, the barrier gas path, and the thickness of carbon paper reduces in time, cause with the conduction of barrier film badly, become the reason that battery performance reduces.
And in the carbon paper manufacture method that the pressurized, heated of not carrying out the precursor fiber sheet of patent documentation 2 record is processed, the thickness of gained carbon paper is to determine according to the situation that the composition of precursor fiber sheet and weight per unit area carry out heat treated.Therefore, be difficult to suitably control the thickness of gained carbon paper.In addition, the composition of precursor fiber sheet and the inequality of weight per unit area can cause directly that the carbon paper thickness and precision reduces, and be not preferred.
The carbon paper of the characteristic that as mentioned above, in the prior art, be difficult to provide fully that the desired ventilation property of carbon paper that satisfies the gas diffuser of the battery that acts as a fuel is high, electroconductibility is high, the residual set amount after the compression is little.
The object of the present invention is to provide a kind of carbon paper, it can be all satisfies simultaneously and was difficult to the desired characteristics of carbon paper to the cell gas diffuser that acts as a fuel that all satisfy simultaneously in the past, specifically, ventilation property is high, electroconductibility is high, the compression after the little characteristic of residual set amount.
Patent documentation 1: Japanese kokai publication hei 9-157052
Patent documentation 2: TOHKEMY 2004-31326
Summary of the invention
The present invention is conceived to the micropore diameter of carbon paper for above-mentioned purpose, finds by suitable its scope of control, and all aspects that can obtain the residual set amount after the ventilation property, electroconductibility, compression of the thickness direction that prior art is difficult to realize are excellent carbon paper all.
The present invention carries out in the molding procedure of hot briquetting processing at the precursor fiber sheet that will contain carbon chopped fiber and thermosetting resin, by using the hot plate moulding that certain intervals is set, can suitably control the micropore diameter of gained carbon paper.
Porous carbon sheet of the present invention is the carbon chopped fiber that will disperse with the bonding porous carbon sheet that obtains of resin carbonation thing, and it is characterized in that: the micropore mould of above-mentioned micropore that has directly is 45～90 μ m, and the fiber diameter of above-mentioned carbon chopped fiber is 5～20 μ m.
In the porous carbon sheet of the present invention, preferably see through 14cm at above-mentioned thickness direction
3/ cm
2/ second air the time differential pressure be 1～10mmAq/mm.
In the porous carbon sheet of the present invention, the volume specific resistance of preferred thickness direction is 30～300m Ω cm.
In the porous carbon sheet of the present invention, the residual set amount (residual set) of preferred thickness direction compression is 3～15 μ m.
In the porous carbon sheet of the present invention, preferred density is 0.15～0.35g/cm
3
In the porous carbon sheet of the present invention, preferred thickness is 100～250 μ m.
In the porous carbon sheet of the present invention, preferably contain the carbonaceous powder.
The manufacture method of porous carbon sheet of the present invention has following operation: the precursor fiber sheet that will contain carbon chopped fiber and thermosetting resin carries out the molding procedure that hot briquetting is processed; To carry out contained thermosetting resin in the precursor fiber sheet that hot briquetting processes and carry out the carbonation process of carbonizing treatment; It is characterized in that: supply with in the precursor fiber sheet of above-mentioned molding procedure, the weight per unit area of above-mentioned carbon chopped fiber is 15～30g/m
2, and the weight per unit area of above-mentioned thermosetting resin is 30～80g/m
2, in the above-mentioned molding procedure, by the above-mentioned precursor fiber sheet of the hot plate moulding that is provided with certain intervals.
In the manufacture method of porous carbon sheet of the present invention, preferred above-mentioned molding procedure comprises following operation: above-mentioned precursor fiber sheet is carried out heating and pressurizing with a pair of hot plate that is in position parallel to each other process.
In the manufacture method of porous carbon sheet of the present invention, in the preferred above-mentioned molding procedure, the interval body that configures in contact by at least one party with above-mentioned hot plate arranges above-mentioned interval.
In the manufacture method of porous carbon sheet of the present invention, in the above-mentioned molding procedure, preferred above-mentioned precursor fiber sheet is sent between the above-mentioned hot plate by phased manner, by this hot plate above-mentioned precursor fiber sheet is carried out heating and pressurizing at the transmission interval and processes.
In the manufacture method of porous carbon sheet of the present invention, preferred above-mentioned molding procedure contains following operation: with two of above-mentioned precursor fiber sheet surfaces with a pair of state with clamping under, one side is introduced continuously the mould with heating unit and slit with this sheet and is carried out hot briquetting on one side.
In the manufacture method of porous carbon sheet of the present invention, the above-mentioned slit of preferred above-mentioned mould is by being arranged by the interval body of pair of metal piece clamping.
In the manufacture method of porous carbon sheet of the present invention, preferred above-mentioned a pair of band is at the layer that has the tool oilness with contacted of above-mentioned mould.
In the manufacture method of porous carbon sheet of the present invention, the above-mentioned slit of preferred above-mentioned mould with above-mentioned a pair of with contacted have the tool oilness the layer.
In the manufacture method of porous carbon sheet of the present invention, preferred above-mentioned a pair of band is endless belt.
In the manufacture method of porous carbon sheet of the present invention, preferably two end span complete cycles of contacted of above-mentioned endless belt and above-mentioned mould the tension force transfer part is set.
In the manufacture method of porous carbon sheet of the present invention, preferably supply with in the above-mentioned precursor fiber sheet of above-mentioned molding procedure, above-mentioned thermosetting resin is 1～3 with respect to the weight ratio of above-mentioned carbon chopped fiber.
In the manufacture method of porous carbon sheet of the present invention, preferably set the above-mentioned interval in the above-mentioned molding procedure, the hot briquetting of above-mentioned molding procedure is processed after, the density of above-mentioned carbon chopped fiber is 0.05～0.10g/cm in the precursor fiber sheet
3, and the density of above-mentioned thermosetting resin be 0.10～0.27g/cm
3
In the manufacture method of porous carbon sheet of the present invention, the fiber diameter of preferably supplying with above-mentioned carbon chopped fiber in the above-mentioned precursor fiber sheet of above-mentioned molding procedure is 5～20 μ m.
In the manufacture method of porous carbon sheet of the present invention, the above-mentioned precursor fiber sheet of preferably supplying with above-mentioned molding procedure contains the carbonaceous powder.
In the manufacture method of porous carbon sheet of the present invention, in the preferred above-mentioned carbonation process, above-mentioned precursor fiber sheet is advanced in the process furnace that keeps inert atmosphere continuously, in this process furnace, with 100～10,000 ℃ of/minute interior heat-up rate of scope is warming up to 1 at least, 200 ℃, during burning till above-mentioned precursor fiber sheet by above-mentioned process furnace, above-mentioned thermosetting resin carbonization is rolled into web-like with the porous carbon sheet that obtains after the above-mentioned carbonation process end.
In the manufacture method of porous carbon sheet of the present invention, preferably in the above-mentioned process furnace of above-mentioned carbonation process, bending part is set, this bending part is used for making the along its length bending on one side of above-mentioned precursor fiber sheet to advance on one side, and this precursor fiber sheet and this bending part limit contact edge are advanced.
In the manufacture method of porous carbon sheet of the present invention, the interior temperature of process furnace that preferably is provided with above-mentioned bending part is 400～2,700 ℃.
In the manufacture method of porous carbon sheet of the present invention, the process furnace that preferably is provided with above-mentioned bending part is the process furnace with 400～800 ℃ of temperature provinces.
In the manufacture method of porous carbon sheet of the present invention, the process furnace that preferably is provided with above-mentioned bending part is the process furnace with 1,600～2,700 ℃ of temperature provinces.
In the manufacture method of porous carbon sheet of the present invention, the angle of bend when preferably making the precursor fiber sheet limit curved edges is advanced along its length by above-mentioned bending part is 5～25 °.
In the manufacture method of porous carbon sheet of the present invention, the two sides contacts with above-mentioned bending part successively in the table of preferred above-mentioned precursor fiber sheet, makes in the table of this precursor fiber sheet the two sides crooked.
Definition and/or its measuring method of the various characteristics value of porous carbon sheet of the present invention are as follows.
(a) the micropore mould of the micropore that has of porous carbon sheet footpath:
The measure of spread that the micropore diameter distribution that porous carbon sheet has is undertaken by mercury penetration method shown below is obtained.The micropore mould footpath of the micropore that porous carbon sheet has distributes according to the micropore diameter of measuring and obtains.
Cut the square coupons of three agreement that contracts a film or TV play to an actor or actress 12mm * 20mm by porous carbon sheet, then precision weighing puts into cell, makes them not overlapping, under reduced pressure injects mercury, measures micropore diameter and distributes.The micropore diameter measure of spread is carried out according to device shown below and condition.Measure number of times for once.During the micropore diameter of measuring distributed, the micropore diameter that distribution proportion is maximum was micropore mould footpath.
Device: Micromeritics company makes, pore sizer 9320
Condition: measure pressure range: about 3.7KPa-207MPa
(→ micro-pore diameter is 70nm～400 μ m approximately)
Mode determination: the process of boosting of above-mentioned pressure range
Pool volume: 5cm
3
(b) fiber diameter of carbon chopped fiber:
From the fiber side photo of 5,000 times of electron microscopes of porous carbon sheet, select arbitrarily 20 carbon chopped fibers, measure its Fibre diameter, ask its simple mean value (Unit Pure mean value).Resin carbonation thing part can be confirmed whether the carbonaceous powder in the electron micrograph by observing.
Differential pressure when (c) making air see through the porous carbon sheet thickness direction:
Mensuration sees through 14cm along the thickness direction of porous carbon sheet
3/ cm
2/ second air the time differential pressure, calculate divided by the thickness of porous carbon sheet.The thickness measuring method of porous carbon sheet as described later.
(d) volume specific resistance of porous carbon sheet thickness direction:
With the mercury electrode clamping of porous carbon sheet with certain area, the volts lost when flowing through certain electric current between electrode is calculated by following formula (I).
The ratio resistance of thickness direction (m Ω cm)=(V * S)/(I * d) (I)
Wherein, V: volts lost (mV)
I: electric current (A)
D: the thickness of porous carbon sheet (cm)
S: the area (cm of mercury electrode
2)
Here, flowing through interelectrode electric current is 1A, and mercury electrode is the circular electrode that uses diameter 3cm.The thickness measuring method of porous carbon sheet as described later.
(e) thickness of porous carbon sheet:
Use the shape of cross section of measuring son to be circular, the diameter micrometer as 5mm, the face that applies 0.15MPa at the thickness direction of sheet is compressed into row and is measured.Measuring point is the lattice point at 1.5cm interval.Measuring number of times is more than 20 times, with its mean value as thickness.
(f) the residual set amount of porous carbon sheet thickness direction compression:
Use above-mentioned micrometer, it is d that the face that applies 0.33MPa at the thickness direction of porous carbon sheet is pressed the thickness of the porous carbon sheet of measuring
1Then the face that applies 1.60MPa at the thickness direction of this sheet is pressed and emission surface is pressed, and repeats altogether twice, and the thickness that then applies this sheet that the face pressure of 0.33MPa measures is d
2, (II) obtains by following formula.Measuring number of times is three times, by its mean value calculation compressed residual deflection.
Compressed residual deflection=d
1-d
2(II)
(g) weight per unit area of porous carbon sheet (weight of unit surface):
Cut the square porous carbon sheet of 10cm * 10cm, measure its weight.Measuring number of times is 10 times, by its mean value calculation.
(h) weight per unit area of carbon chopped fiber:
Identical with the situation of porous carbon sheet, the mensuration of the weight per unit area of carbon chopped fiber is in atmosphere, under 400 ℃ the carbon chopped fiber sheet before the impregnation thermosetting resin to be heated 8 hours, stays carbon chopped fiber, makes the thermolysiss such as caking agent in addition.
(i) weight per unit area of thermosetting resin:
The variable quantity that is contained resin pickup front and back weight per unit area by the carbon chopped fiber sheet calculates.
Contain that the weight per unit area of carbon chopped fiber sheet is to carry out 5 minutes heat treated at 160 ℃ behind the resin pickup, resin solidification is measured.
(j) density of porous carbon sheet:
Density refers to apparent density.Thickness and weight per unit area by above-mentioned porous carbon sheet are calculated.
(k) thermosetting resin is with respect to the weight ratio of carbon chopped fiber:
Weight per unit area by thermosetting resin is with respect to the recently calculating of the weight per unit area of above-mentioned carbon chopped fiber.
(l) in the molding procedure, the density of carbon chopped fiber contained in the rear precursor fiber sheet and the density of thermosetting resin are processed in hot briquetting:
The afterwards THICKNESS CALCULATION of precursor fiber sheet is processed in weight per unit area and hot briquetting by above-mentioned carbon chopped fiber and thermosetting resin.Here the measuring method of the thickness of the thickness of employed precursor fiber sheet and porous carbon sheet is measured equally.
Heat-up rate when (m) the precursor fiber sheet burns till:
According to following (III) formula, the sheet that imports by the top temperature in process furnace temperature in, the process furnace, by the process furnace entrance moves to the needed time of highest temperature region (traveling time) and obtains.Here, the process furnace entrance refers to that atmosphere is switched to the position of the process furnace inlet side of inert atmosphere by atmosphere.
V＝(T2-T1)/t (III)
Here, V: heat-up rate (℃/minute), T1: the temperature of process furnace entrance (℃), T2: the top temperature in the process furnace (℃), t: traveling time (minute)
Process furnace needn't be 1, also can carry out multistep by the process furnace more than 2 and burn till.When using 2 process furnace, the heat-up rate of the 1st step process furnace is obtained by following formula (III), the heat-up rate of the 2nd step process furnace be make the T1 of following formula (III) be the top temperature of front step process furnace, namely the 1st top temperature that goes on foot process furnace is obtained.Situation when using 3 above process furnace too.
(n) angle of bend of precursor fiber sheet:
The direct of travel angulation of the position precursor fiber sheet that to be the precursor fiber sheet of advancing leave bending part at direct of travel and precursor fiber sheet with the contacted position of bending part precursor fiber sheet, craspedodrome is 0 °, the U-shaped turnover is 180 °.
Description of drawings
Fig. 1 is the figure that the micropore diameter of an embodiment (porous carbon sheet shown in Figure 2) of expression porous carbon sheet of the present invention distributes.
Fig. 2 is the surface electronic microphotograph (250 times of multiplying powers) of an embodiment of porous carbon sheet of the present invention.
Fig. 3 is the process picture sheet of a scheme of the manufacturing process of employing during the manufacture method of expression porous carbon sheet of the present invention is implemented.
Fig. 4 is the schematic perspective view of the shaped device of a scheme (the 1st forming method) of the molding procedure of employing during the manufacture method of porous carbon sheet of the present invention is implemented.
Fig. 5 is the vertical section schematic diagram of the shaped device of another scheme (the 2nd forming method) of the molding procedure of employing during the manufacture method of porous carbon sheet of the present invention is implemented.
Fig. 6 is the vertical section schematic diagram of a scheme of molding procedure in the past the porous carbon sheet manufacturing process, and to treatment step that should operation and the schematic diagram of the course of the temperature and pressure that the precursor fiber sheet that shows bears.
Fig. 7 is the vertical section schematic diagram of a scheme (the 1st forming method) of molding procedure in the porous carbon sheet of the present invention manufacturing process, and to treatment step that should operation and the schematic diagram of the course of the temperature and pressure that the above-mentioned precursor fiber sheet that shows bears.
Fig. 8 is the vertical section schematic diagram of a scheme (the 2nd forming method) of molding procedure in the porous carbon sheet of the present invention manufacturing process, and to treatment step that should operation and the schematic diagram of the course of the temperature and pressure that the above-mentioned precursor fiber sheet that shows bears.
Fig. 9 is the shaped device vertical section schematic diagram of a scheme (the 2nd forming method) of molding procedure in the manufacturing process of porous carbon sheet of the present invention.
Figure 10 is the partial cross section figure of the A-A ' face of Fig. 9.
Figure 11 is the schematic cross-section of a scheme of the metal block that uses in the shaped device of a scheme (the 2nd forming method) of molding procedure in the manufacturing process of porous carbon sheet of the present invention.
Figure 12 is the side elevational view of an example of the case of bending of the sheet that carries out of the bending part that uses in the scheme of expression by firing process in the porous carbon sheet of the present invention manufacturing process.
Figure 13 is the side elevational view of another example of the case of bending of the sheet that carries out of the bending part that uses in the scheme of expression by firing process in the porous carbon sheet of the present invention manufacturing process.
Figure 14 is the side elevational view of another example of the case of bending of the sheet that carries out of the bending part that uses in the scheme of expression by firing process in the porous carbon sheet of the present invention manufacturing process.
Figure 15 is the side elevational view of the angle of bend of sheet in the bending part that uses in the scheme of firing process in the manufacturing process of explanation porous carbon sheet of the present invention.
Figure 16 is the side elevational view of an example of the ladder sigmoid parts that use in the scheme of firing process in the manufacturing process of porous carbon sheet of the present invention.
Figure 17 is the horizontal bar sectional view of the bending part of Figure 16.
Embodiment
Figure 2 shows that the electron micrograph on surface of an embodiment of porous carbon sheet 11 of the present invention.Figure 3 shows that a scheme of the manufacturing process of porous carbon sheet shown in Figure 2 11.Figure 4 shows that a scheme of molding procedure 23 in the manufacturing process shown in Figure 3.
Among Fig. 2, porous carbon sheet 11 of the present invention contains the many carbon chopped fibers 12 of dispersion state of visible wire and the resin carbonation thing 13 of bonding carbon chopped fiber 12.This porous carbon sheet 11 has the particulate carbonaceous powder 14 that is scattered in the resin carbonation thing 13 and exists.
The state of the dispersion of carbon chopped fiber 12 refers to that carbon chopped fiber 12 does not have the orientation of significant certain orientation in 11 of porous carbon sheets, roughly be randomly, the state that for example exists in random direction.A concrete example is: the state that the staple fibre that can see in the staple fibre sheet by the method manufacturing of manufacturing paper with pulp described later disperses.
The micropore diameter of carbon paper (porous carbon sheet 11) is by the carbon fiber decision as the carbon paper structural framework, and in the carbon paper, when the density of the carbon fiber that unit volume exists was high, micropore diameter was little; When the density of the carbon fiber that unit volume exists was low, micropore diameter was large.
Consider from above-mentioned angle, the density of the carbon fiber that above-mentioned patent documentation 1 described carbon paper unit volume exists is high, and namely micropore diameter is little.Therefore can think: the compress variation of thickness direction is little, but the ratio resistance of the ventilation property of thickness direction and thickness direction becomes to accept or reject choice relation.
The density of the carbon fiber that above-mentioned patent documentation 2 described carbon paper unit volumes exist is low, and namely micropore diameter is large.Therefore, low by the resistivity of face, ventilation property is high, but the compress variation of thickness direction is large.
The present invention is conceived to the micropore diameter of carbon paper, and discovery can obtain the equal excellent carbon paper in ventilation property, electroconductibility, all aspects of compress variation on the difficult in the prior art thickness direction by suitably controlling its scope.
The micropore mould of the micropore that porous carbon sheet 11 of the present invention has porous carbon sheet 11 by manufacture method described later directly is controlled at the scope of 45～90 μ m, can all satisfy simultaneously thus the required characteristics of carbon paper that in the past were difficult to the cell gas diffusers that act as a fuel that all satisfy simultaneously, namely ventilation property is high, electroconductibility is high, the residual set amount after the compression is little.
If micropore mould footpath is less than 45 μ m, then the residual set amount of the compression of thickness direction generation reduces, but the volume specific resistance of the air permeance resistance of thickness direction and thickness direction becomes to accept or reject choice relation.If micropore mould footpath is greater than 90 μ m, then the volume specific resistance of the air permeance resistance of thickness direction and thickness direction reduces, but the residual set amount that the compression of thickness direction produces increases.
The micropore mould that porous carbon sheet 11 has directly is preferably 50～80 μ m, more preferably 55～70 μ m, more preferably 55～65 μ m.
The micropore diameter result's of the porous carbon sheet 11 of measuring by mercury penetration method a example as shown in Figure 1.Among Fig. 1, transverse axis X represents micropore diameter [unit: μ m], and longitudinal axis Y represents the differential value [unit: cc/glog nm] of micropore volume, i.e. expression has the ratio of the micropore of this micropore diameter.Among Fig. 1, curve 1 expression is with respect to the ratio (longitudinal axis Y) of the micropore of the porous carbon sheet 11 of micropore diameter (transverse axis X).In the curve 1 of the micropore ratio of expression porous carbon sheet 11, the micropore diameter that the point of the differential value maximum of micropore volume (the position 1a among the transverse axis X that dots among the figure) is located is micropore mould footpath.
In order to obtain suitable micropore mould footpath, the fiber diameter of the carbon chopped fiber 12 of formation porous carbon sheet 11 is in the scope of 5～20 μ m.The fiber diameter of carbon chopped fiber 12 is preferably 6～13 μ m, more preferably 6～10 μ m.
The carbon fiber that consists of carbon chopped fiber 12 can use that polyacrylonitrile (PAN) is, the carbon fiber of asphalt series, artificial silk system etc.Wherein, preferably use PAN system or asphalt series, the particularly carbon fiber of PAN system, because their physical strengths are excellent, and have appropriate flexibility, can obtain the porous carbon sheet of operability excellence.
If above-mentioned differential pressure is below the 10mmAq/mm, can prevent with high output density operating fuel cell the time that then the battery performance that the obstruction of the water that generates causes from reducing.If above-mentioned differential pressure is more than the 1mmAq/mm, can prevent that then the proton-conducting that the solid polyelectrolyte membrane drying causes from reducing.
The volume specific resistance of porous carbon sheet 11 thickness directions is preferably below the 300m Ω cm, more preferably below the 200m Ω cm, more preferably below the 150m Ω cm.
If volume specific resistance is below the 300m Ω cm, then can suppresses the battery performance that the ohmic loss of gas diffuser causes and reduce.The volume specific resistance of thickness direction is more little more can to reduce ohmic loss, as long as but take with the resin carbonation thing the bonding vesicular structure that obtains of carbon chopped fiber, then be its limit about 30m Ω cm.
The residual set amount that the compression of porous carbon sheet 11 thickness directions produces is preferably below the 15 μ m, more preferably below the 12 μ m, more preferably below the 8 μ m.
Usually, the gas diffuser take porous carbon sheet as base material is that they are engaged with the solid polyelectrolyte membrane that has catalyst layer on the two sides, consists of film-electrode bond.In the both sides of this film-electrode bond across pad (gasket) with establishing fluted barrier film clamping, this groove is the necessary gas passage of reaction, and a plurality of these structures are stacked, the formation polymer electrolyte fuel cell.
If the residual set amount that the compression of porous carbon sheet thickness direction produces is greater than 15 μ m, then the gas diffuser take porous carbon sheet as base material can drop in the groove that is located on the barrier film, stop up the gas passage, the thickness of gas diffuser reduces in time, cause with the conduction of barrier film badly, become the reason that battery performance reduces.Porous carbon sheet 11 is porous materials, even can reduce the residual set amount of its through-thickness compression, the residual set amount still has the limit about 3 μ m.
The density of porous carbon sheet 11 is preferably 0.15～0.35g/cm
3, 0.18～0.32g/cm more preferably
3, 0.20～0.30g/cm more preferably
3
If density is 0.35g/cm
3Below, then the space of porous carbon sheet 11 increases, and ventilation property improves, and during therefore with high output density operating fuel cell, can prevent that the battery performance that the obstruction of the water that generates causes from reducing.Density is 0.15g/cm
3Above, can prevent that then ventilation property from excessively increasing, solid polyelectrolyte membrane is dry, and proton-conducting reduces.
The thickness of porous carbon sheet 11 is preferably 100～250 μ m, more preferably 110～240 μ m, more preferably 120～230 μ m.The thickness of porous carbon sheet 11 during with shear action porous carbon sheet 11 break or flexibility relevant.
Thickness is lower than 100 μ m, then uses with in the fuel cell of porous carbon sheet as the gas diffuser manufacturing of base material, and when porous carbon sheet stood from the shearing force of barrier film, porous carbon sheet was easily destroyed.When thickness surpassed 250 μ m, the flexibility of porous carbon sheet significantly reduced, and is difficult to be rolled into the web-like of porous carbon sheet described later.
Figure 3 shows that a scheme of the manufacturing process of porous carbon sheet of the present invention.Among Fig. 3, the manufacturing process of porous carbon sheet comprises: machine hand's order 21 of moulding carbon chopped fiber sheet; The resin impregnated operation 22 of impregnation thermosetting resin in the carbon chopped fiber sheet of moulding; With impregnation the carbon chopped fiber sheet of resin (precursor fiber sheet) carry out the molding procedure 23 that hot briquetting is processed; And will carry out the carbonation process 24 that contained thermosetting resin in the precursor fiber sheet that hot briquetting processes carries out carbonizing treatment.
In the manufacturing process of porous carbon sheet of the present invention, the weight per unit area of the above-mentioned carbon chopped fiber in the above-mentioned precursor fiber sheet is l 5～30g/m
2, the weight per unit area of above-mentioned thermosetting resin is 30～80g/m
2And in the above-mentioned molding procedure 23, above-mentioned precursor fiber sheet carries out hot briquetting by the hot plate that is provided with certain intervals to be processed.
In the manufacture method of porous carbon sheet of the present invention, the micropore mould of porous carbon sheet of the present invention directly is controlled at suitable scope.As a result, can make the equal excellent porous carbon sheet of the present invention 11 in all aspects of residual set amount after the ventilation property, electroconductibility, compression of the thickness direction that prior art is difficult to make.
The micropore diameter of porous carbon sheet can be controlled by the precursor fiber sheet being carried out the pressure of heating and pressurizing when processing, wherein said precursor fiber sheet be in carbon fiber paper impregnation the precursor fiber sheet of thermosetting resin.For example, above-mentioned patent documentation 1 described carbon paper is by the precursor fiber sheet is realized little micropore diameter with suitable exert pressure, wherein, described precursor fiber sheet be in the high carbon fiber paper of weight per unit area impregnation the precursor fiber sheet of thermosetting resin.
In order to enlarge micropore diameter, can consider will be in the low carbon fiber paper of weight per unit area impregnation the precursor fiber sheet of thermosetting resin under low pressure carry out heating and pressurizing and process.But even the heating and pressurizing of this precursor fiber sheet low pressure is processed, the thickness variation rate is also large before and after processing, and the heating and pressurizing of simple low pressure is processed and is difficult to be controlled to be target thickness.
Therefore, can think that above-mentioned patent documentation 2 described carbon papers are the precursor fiber sheet not to be carried out heating and pressurizing to process, only realize large micropore diameter by heat treated, wherein, described precursor fiber sheet is the precursor fiber sheet of impregnation graphite granule and thermosetting resin in the low carbon fiber paper of weight per unit area.But in the manufacture method of not carrying out the heating and pressurizing processing, the thickness of gained carbon paper determines according to circumstances according to composition and the weight per unit area of precursor fiber sheet, therefore is difficult to suitably control the thickness of gained carbon paper.The composition of precursor fiber sheet and weight per unit area inequality can directly cause the thickness and precision of carbon paper to reduce, and be therefore not preferred.
The manufacture method of porous carbon sheet of the present invention is based on following discovery: in the precursor fiber sheet that contains carbon chopped fiber and thermosetting resin being carried out the molding procedure 23 that hot briquetting processes, by coming moulding with the hot plate that is provided with certain intervals, can suitably control the micropore diameter of the porous carbon sheet of difficulty in the prior art.
Above-mentioned precursor fiber sheet can be made by machine hand's order 21 shown in Figure 3 and resin impregnated operation 22.
In machine hand's order 21, the carbon chopped fiber that is cut into suitable length is evenly spread in the water, the carbon chopped fiber that disperses is manufactured paper with pulp on the net, the carbon chopped fiber sheet of manufacturing paper with pulp is immersed in the aqueous dispersion of polyvinyl alcohol, the sheet of dipping is mentioned and drying.Above-mentioned polyvinyl alcohol plays the caking agent effect of bonding carbon chopped fiber, under the state that carbon chopped fiber disperses, can make them by the carbon chopped fiber sheet of the bonding state of caking agent.
In the resin impregnated operation 22, the carbon chopped fiber sheet that will make in machine hand's order 21 is immersed in the solution of thermosetting resin, and the sheet of dipping is mentioned, and 90 ℃ of dryings 3 minutes, can make the precursor fiber sheet thus.
In resin impregnated operation 22, be scattered in the solution of thermosetting resin by making the carbonaceous powder, can make and contain carbonaceous powder 14 in the porous carbon sheet 11.
With respect to 100 parts by weight resin, the carbonaceous powder is preferably 5～100 weight parts, more preferably 10～90 weight parts, more preferably 15～70 weight parts.When the carbonaceous powder lacked than 5 weight parts, in continous way carbonation process 24 described later, the crackle of the resin carbonation thing 13 that the rapid Carbonization contract of thermosetting resin causes increases, and was therefore not preferred.When the carbonaceous powder manyed than 100 weight parts, being used for the necessary thermosetting resin of bonding carbonaceous powder increased, and the amount that is used for the thermosetting resin of bonding carbon chopped fiber reduces, and is therefore not preferred.
In the molding procedure 23, by the hot plate that is provided with certain intervals above-mentioned precursor fiber sheet is carried out hot briquetting and process.Fig. 4 represents to implement a scheme---the schematic perspective view of an example of the shaped device of the 1st forming method of molding procedure 23 in the manufacturing process of porous carbon sheet of the present invention.Use thermocompressor 32 in the 1st forming method.
Among Fig. 4, thermocompressor 32 has upside hot plate 33 and downside hot plate 34.Upside hot plate 33 and downside hot plate 34 wherein any one party or both sides can move by above-below direction, and the diagram of its travel mechanism is omitted.In the thermocompressor 32 shown in Figure 4, downside hot plate 34 is fixed, and upside hot plate 33 moves up and down shown in arrow 33a with respect to downside hot plate 34.Place precursor fiber sheet 31 below upside hot plate 33 and between above the downside hot plate 34.Precursor fiber sheet 31 below upside hot plate 33 and between above the downside hot plate 34 owing to the decline of upside hot plate 33 be clamped in upside hot plate 33 below and downside hot plate 34 above between.
In above-mentioned the 1st forming method, the formation method that is arranged at the certain intervals between hot plate has two kinds.The 1st kind of method is to regulate movable upside hot plate 33 with respect to the mobile stroke (stroke) of downside hot plate 34, forms required interval.The 2nd kind of method is the left and right sides outer fix of precursor fiber sheet 31 present positions on downside hot plate 34, the interval body 35 that setting is fixed on the top of downside hot plate 34 or can freely changes contacts above the following and interval body 35 by upside hot plate 33 movably and forms required interval.Interval body 35 also can be installed in upside hot plate 33 following with replace being installed in downside hot plate 34 above.Consider from the precision aspect of being located at the interval between hot plate, preferably adopt the second method of interval body 35.
As previously mentioned, in the manufacture method of porous carbon sheet 11 of the present invention, the weight per unit area of the carbon chopped fiber of above-mentioned precursor fiber sheet is 15～30g/m
2, the weight per unit area of thermosetting resin is 30～80g/m
2
If the weight per unit area of carbon chopped fiber 12 is 15g/m
2Above, then the residual set amount of the moulding of the thickness direction of porous carbon sheet 11 generation reduces, and is therefore preferred.If the weight per unit area of carbon chopped fiber 12 is 30g/m
2Below, then resin carbonation thing 13 increases with respect to the ratio of carbon chopped fiber 12, and the volume specific resistance of sheet 11 thickness directions reduces, and is therefore preferred.
If the weight per unit area of thermosetting resin is 30g/m
2Above, then the amount of the resin carbonation thing 13 of bonding carbon chopped fiber 12 increases, and the volume specific resistance of porous carbon sheet 11 thickness directions reduces, and is therefore preferred.If the weight per unit area of thermosetting resin is 80g/m
2Below, then sheet 11 can not filled up by resin carbonation thing 13, can guarantee sufficient hole, and the ventilation property of thickness direction improves, and is therefore preferred.
In above-mentioned the 1st forming method, preferably by with at least one party of upside hot plate 33, downside hot plate 34 in contact configuration space body 35 above-mentioned interval is set.By using interval body 35, though upside hot plate 33, when downside hot plate 34 tilts, also can be easily and set accurately the interval by interval body 35.
In above-mentioned the 1st forming method, preferably precursor fiber sheet 31 is sent to by phased manner between upside hot plate 33 and the downside hot plate 34, is transmitting interval, carry out heating and pressurizing by upside hot plate 33 and 34 pairs of precursor fiber sheets of downside hot plate 31 and process.Among Fig. 4, the delivery direction of precursor fiber sheet 31 is as shown in arrow 30.Precursor fiber sheet 31 is transmitted by phased manner, the interval of advancing at precursor fiber sheet 3l carries out the heating and pressurizing processing to precursor fiber sheet 31, need not thus precursor fiber sheet 31 is cut into fragment (piece Leaf) (sheet with certain-length, width), can carry out heating and pressurizing with the form of lengthy motion picture and process.
In the molding procedure 23, heat under the state to precursor fiber sheet pressurization, make thermosetting resin curedly, it is necessary making the carbon chopped fiber that is in dispersion state bonding by the thermosetting resin that solidifies.Therefore, if under non-pressurized state the heat hot thermosetting resin, then carbon chopped fiber and thermosetting resin can not be fully bonding, the problems such as precursor fiber sheet thickness and precision variation after the molding procedure occur.
Figure 6 shows that the schematic cross-section of a scheme of molding procedure in the porous carbon sheet manufacturing process in the past and to treatment step that should operation and the schematic diagram (graph) of the temperature and pressure course that the precursor fiber sheet that shows bears.Figure 7 shows that the schematic cross-section of above-mentioned the 1st forming method and to treatment step that should operation and the schematic diagram of the temperature and pressure course that the precursor fiber sheet that shows bears.
Fig. 6 is the vertical section schematic diagram of the disclosed molding procedure of WO01/56103A.Among Fig. 6, use biobelt pressurizing device 52 in order to carry out continuously shaped, transmit the sheet 51 that contains carbon chopped fiber and thermosetting resin with a pair of endless belt 53,54 pairs of sheets 51 carry out preheating in the preheating zone simultaneously, then carry out heating and pressurizing by 55 pairs of sheets 51 of roll squeezer (roll press), obtain the products formed 56 of precursor fiber sheet 51.The delivery direction of sheet 51 and products formed 56 (direct of travel) is as shown in arrow 50.
The below of the biobelt pressurizing device 52 of Fig. 6 is depicted as the course figure that acts on the temperature and pressure of sheet 51 in this device 52.The transverse axis T i of this figure represents sheet 51 by the traveling time of device 52 entrance to outlet, and longitudinal axis Te-P represents that migration along with sheet 51 is in the state of the temperature and pressure of sheet 51.In the drawings, the variation of temperature represents with solid line Te, and the variation with dashed lines P of pressure represents.Sheet is preheated in the interval 51 shown in the arrow P reHe.Sheet 51 is heated pressurization in the position of arrow HePr.
But in the biobelt pressurizing device 52, heating is to carry out between the roll squeezer 55 in preheating zone 54, and pressurization is only undertaken by the line pressure of roll squeezer 55 with the utmost point short period of time.Therefore, in the moulding of being undertaken by biobelt pressurizing device 52, compare with the intermittent type platen-press that uses in the past the segment-like porous carbon sheet method for making, can only obtain the poor products formed of thickness and precision.
Figure 7 shows that the interruption pressurizing device 62 of implementing above-mentioned the 1st forming method in the manufacture method of porous carbon sheet 11 of the present invention.Be interrupted pressurizing device 62 and have the platen-press that contains face 63 and lower face 64.In the platen-press, upper face 63 moves up and down with respect to lower face 64 as shown in arrow 66ly.Move up and down by this, platen-press opens and closes repeatedly.During platen-press was opened, precursor fiber sheet 61 and products formed 65 transmitted along the direction shown in the arrow 60.After the transmission of sheet 61 stopped, platen-press was closed, and sheet 61 is heated pressurization.After this heating and pressurizing, platen-press is opened, and the transmission of sheet 61 begins again, and products formed 65 is transported from be interrupted pressurizing device 62.
The below of the interruption pressurizing device 62 of Fig. 7 is depicted as the figure of the temperature and pressure course that acts on the precursor fiber sheet 61 in this device 62.The transverse axis T i of this figure represents the traveling time that sheet 61 is extremely exported by the entrance that installs 62, and longitudinal axis Te-P represents to act on along with moving of sheet 61 state of the temperature and pressure of sheet 61.Among the figure, the variation of temperature represents with solid line Te, and the variation with dashed lines P of pressure represents.Sheet 61 is heated in the interval shown in the arrow He.Sheet 61 is heated pressurization in the position of arrow P r.The state of four discontinuity pressurizations is carried out in expression among this figure.
Be interrupted in the pressurizing device 62, heating is that the entrance at press carries out between outlet, pressurization be during opening, transmit products formed 65 except Flat pressure machine, the state of pressing with load surface carries out.Therefore, be interrupted in the extrusion forming, compare with the biobelt press of Fig. 6, can fully guarantee the time with the pressurized state heating, therefore can obtain having the products formed 65 of more excellent thickness and precision.
But even by being interrupted the pressurizing device moulding, during opening platen-press, transmitting products formed, resin is cured under uninflated state, therefore can only obtain the products formed with the thickness and precision of in the past the dull and stereotyped pressurizing device same degree of intermittent type.
Figure 8 shows that the mould band shaped device (ダ ィ ス ベ Le ト building mortion) 75 of implementing above-mentioned the 2nd forming method in the porous carbon sheet manufacture method of the present invention.Mould band shaped device 75 has advance a pair of and is with 73 and warmed-up mould 74.A pair ofly be with 73 according to direction continuous moving shown in the arrow 70.This moves in the way, a pair ofly is with 73 by mould 74.Precursor fiber sheet 72 is clamped in a pair of being with in the middle of 73, is with 73 along direction continuous moving shown in the arrow 70 with a pair of.This moves in the way, and precursor fiber sheet 72 is with 73 by mould 74 with a pair of.Be clamped in a pair of with the precursor fiber sheet 72 in 73 by during the mould 74, precursor fiber sheet 72 is carried out hot briquetting and processes.Process by this hot briquetting, the bonding of carbon chopped fiber and thermosetting resin occurs in precursor fiber sheet 72 thermosetting resin cured, passed through mould 74 by in a pair of precursor fiber sheet 72 with 73 clampings, thermosetting resin cured, obtain being shaped to the precursor fiber sheet 71 of desired thickness.
Mould band shaped device 75 belows of Fig. 8 are depicted as the temperature and pressure course figure that acts on sheet 72 in this device 75.The transverse axis T i of this figure represents the traveling time that sheet 72 is extremely exported by the entrance that installs 75, and longitudinal axis Te-P represents to act on along with moving of sheet 72 state of the temperature and pressure of sheet 72.Among the figure, the variation of temperature represents with solid line Te, and the variation with dashed lines P of pressure represents.Sheet 72 is heated in the interval that arrow He represents.Sheet 72 is in the interval moulding shown in the arrow P r.That is, be heated moulding at these two interval sheets 72.Therefore, in the moulding of being undertaken by mould band shaped device 75, always to keep certain thickness state heating, therefore can obtain having the products formed 65 of more excellent thickness and precision.
Fig. 5 is a scheme---the mould 74 of the mould band shaped device 75 shown in Figure 8 of the 2nd forming method and near the amplification schematic cross-section thereof for the porous carbon sheet of the present invention manufacturing process molding procedure 23 of implementing above-mentioned explanation.
Among Fig. 5, mould band shaped device 45 comprises a pair ofly is with 43 and mould 44, and described mould 44 has a pair of with the 43 slit 44SL that advance and pass through.Mould 44 has the device (not shown) that heats it.Precursor fiber sheet 42 is advanced a pair ofly is with 43 clampings, with being introduced in continuously among the slit 44SL of mould 44 with 43, is heated simultaneously moulding.Through the precursor fiber sheet 42 of hot briquetting, thermosetting resin cured, become the precursor fiber sheet 41 that is shaped to desired thickness, be with 43 to be drawn by mould 44 with a pair of, move by direction shown in the arrow 40.
Among Fig. 5, can not be attached to because of the curing of thermosetting resin on the mould 44 in order to make precursor fiber sheet 42, can make a pair of width with 43 Width sheet 42 large.That is, so that sheet 42 its whole face always by a pair of with 43 states that cover under by mould 44.
The length of mould 44 on precursor fiber sheet 42 direct of travels is preferably 5～100cm, more preferably 10～80cm, further preferred 30～60cm.If the length of mould 44, then contains the time shorten that the sheet 42 of carbon chopped fiber and thermosetting resin is heated by mould 44 less than 5cm, thermosetting resin can not fully solidify sometimes.In addition, a pair of with 43 required overtensions if the length of mould 44 greater than 100cm, then drives.Preferably the width than the precursor fiber sheet 42 of wanting moulding is large to be located at the width of slit 44SL of mould 44.
Preferred 120～300 ℃ of the Heating temperature of mould 44, more preferably 160～280 ℃, further preferred 180～260 ℃.If Heating temperature is lower than 120 ℃, then the speed of response of thermosetting resin reduces sometimes.If Heating temperature is higher than 300 ℃, then described later have release property, oilness the layer in contained fluoro-resin generation melting, thermolysis.The heating unit of mould 44 can use and the same heating unit that uses in common platen-press and roll-in.
The long preferred 3～20mm of the fiber of carbon chopped fiber, further preferred 5～15mm.The fiber length of carbon chopped fiber is in these scopes, then in machine hand's order 21, making carbon chopped fiber disperse, copy paper, when obtaining the carbon chopped fiber sheet, can improve the dispersiveness of carbon chopped fiber, can suppress the inhomogeneous of weight per unit area.
As thermosetting resin, such as using resol, melamine resin, urea resin and Resins, epoxy etc., preferably use the high resol of carbonization rate when under inert atmosphere, heating.
Intermittent pressurized, biobelt pressurization etc. are by in the method for pressure-controlling precursor fiber sheet thickness, and the inequality of carbon chopped fiber, thermosetting resin weight per unit area is directly related with the uneven thickness of the precursor fiber sheet of moulding.
In the manufacture method of porous carbon sheet of the present invention, the thickness of precursor fiber sheet is not by pressure but passes through Separation control.Therefore, even the inhomogeneous material of applying unit area weight, the part that weight per unit area is high applies high pressure, part that weight per unit area is low applies low pressure, can obtain the high precursor fiber sheet of thickness and precision.
The interval that is arranged at the slit 44SL of mould 44 be preferably a pair of multiply by respectively with 43 thickness and the thickness of precursor fiber sheet 42 after moulding of wanting moulding 0.5～1.5 coefficient gained with.The coefficient that the thickness of sheet 42 is taken advantage of must be regulated according to the kind of employed carbon chopped fiber, thermosetting resin or amount, preferably in 0.5～1.5 range regulation, can obtain thus the precursor fiber sheet 41 of desired thickness.
As shown in Figure 5, above-mentioned the 2nd forming method is under the state that always keeps certain intervals the precursor fiber sheet to be heated, and makes thermosetting resin curedly, makes carbon chopped fiber bonding.Therefore, than the method for in the past the long products formed of acquisition---the biobelt pressurization or as the manufacture method with precursor fiber sheet heated time band under non-pressurized state of above-mentioned the 1st forming method etc. more can obtain the high long precursor fiber sheet of thickness and precision.
In the method that obtains segment-like precursor fiber sheet---in the intermittent pressurized, the size of press face is necessary for the size of the precursor fiber sheet of wanting moulding or larger, and therefore, in order to obtain long products formed, pressurizing device must be extensive.In addition, along with the precursor fiber sheet of wanting moulding increases, also must increase the size of press face, keep the parallelism difficult of press face, so the thickness and precision variation of gained precursor fiber sheet.
In above-mentioned the 2nd forming method, directly do not contact with mould 44 in order to make precursor fiber sheet 42, the width of mould 44 is necessary for the width of precursor fiber sheet 42 of moulding or wider; Carry out continuously hot briquetting because precursor fiber sheet 42 limits are introduced on the limit, so the length of mould 44 on precursor fiber sheet 42 direct of travels can be shorter than precursor fiber sheet 42.Therefore, the parallelism of being located at the slit 44SL of mould 44 easily keeps, and can obtain the long precursor fiber sheet with higher thickness and precision that obtains than intermittent pressurized.
Fig. 9 is a pair of with the 43 vertical section schematic diagram for the mould band shaped device of a pair of endless belt in the mould band shaped device 45 shown in Figure 5.Figure 10 is the A-A ' cross-sectional view of Fig. 9.Among Fig. 9 and Figure 10, mould band shaped device 87 comprise a pair of endless belt 84, rotating band 84 drive unit 86, have the mould 83 with the 84 slit 83SL that pass through.Mould 83 has the device (not shown) that heats it.Become thermosetting resin cured and precursor fiber sheet 81 moulding moves with the direction of a pair of endless belt 84 according to arrow 80 through the precursor fiber sheet 82 of hot briquetting.
Among Fig. 9 and Figure 10, mould 83 is formed by pair of metal piece 83a, 83b.The slit 83SL of mould 83 forms by the interval body 83SP that is located between pair of metal piece 83a, the 83b.By selecting the height of interval body 83SP, the size that can regulate the interval of mould 83.By using this interval body, just need not to prepare different moulds 83 according to the precursor fiber sheet 81 required thickness after each moulding.Can carry out in addition assembling, the decomposition of mould 83, therefore can make a pair of band that transmits the precursor fiber sheet is endless belt.
The ironing (pultrusion method) same with above-mentioned the 2nd forming method, that the reinforcing fiber that will contain in addition thermosetting resin is pulled out from the mould of heating.In this ironing, the gained products formed is applied tension force, pull out.Therefore in order to make products formed can because tension force destroys, must not make reinforcing fiber in the length direction orientation of products formed.
In above-mentioned the 2nd forming method, will contain the precursor sheet of carbon chopped fiber and thermosetting resin with a pair of band clamping, carry out hot briquetting in the mould with slit while be incorporated into.Therefore, necessary tension force imposes on band when introducing this sheet, therefore also can carry out hot briquetting by the precursor fiber ironing moulding, a little less than orientation, length direction the in the longitudinal direction stretching resistance of reinforcing fiber to being difficult to.
A pair ofly preferably with 42 contacted of precursor fiber sheets the layer with release property is being set with 43.The layer that has release property by existence, can prevent when thermosetting resin from solidifying by heating with 43 adhesion.Layer with release property is preferably the layer that contains fluoro-resin.
A pair of with 43 layers that preferably have oilness the face that contacts with mould 44 setting.Owing to precursor fiber sheet 42 is introduced the slit that is arranged at mould 44, therefore must have than hightension.Have the layer of oilness by setting, can reduce the friction with mould 44, can reduce necessary tension force.
For reduce a pair of with 43 with the friction of mould 44, can the slit of mould 44 and a pair of with 43 face that contact settings have oilness layer.
The layer with oilness that is arranged on the mould 44 preferably contains packing material.Have the layer of oilness by containing packing material, the wearability with layer of oilness improves.If have the layer of oilness owing to friction is worn and torn, then the interval of the slit 43SL of mould 44 changes, and can't obtain the precursor fiber sheet of desired thickness.
Layer with oilness is preferably the layer that contains fluoro-resin.Specifically, have by baking (the baked I is paid け), in the method for the surface coated fluoro-resin of being with the contacted mould 44 that slides.
Fluoro-resin refers to that tetrafluoroethylene resin (PTFE), perfluoroalkoxy resin (PFA), fluoroethylenepropyl.ne resin (FEP) and fluorinated ethylene tetrafluoroethylene resin (ETFE) etc. contain the resin of fluorine atom at molecule.
The contained packing material of layer with oilness can use carbon fiber, glass fibre, granular graphite, bronze and molybdenumdisulphide etc.
Figure 11 is the side elevational view of a distortion example of a metal block among pair of metal piece 83a, the 83b of mould 83 of Fig. 9.Among Figure 11, metal block 101 has the fluoro-resin sheet 103 that contains packing material that is attached to its side, and these sheet 103 usefulness retaining plates 102 are fixing.By using the removable fluoro-resin sheet 103 that contains packing material, can make maintainability than the more excellent metal block of situation that comes fluorine resin coating by sintering.
A pair ofly can use the sheet that contains glasscloth and fluoro-resin with 43.The sheet that can also use two surfaces with fluoro-resin coated metal sheet to obtain.
As shown in Figures 9 and 10, a pair ofly be with 43 to be preferably a pair of endless belt 84.By making band for endless belt, precursor fiber sheet 81 that can the moulding random length.
Preferably at a pair of endless belt 84 and two ends 83 contacted of moulds, stride complete cycle tension force transfer part 85 is set.According to width, the thickness of the products formed 81 of wanting moulding, must apply large tension force to a pair of endless belt 84.To the endless belt transferring power several method is arranged.
When pinching (nip) endless belt and carry out transmission of power by driving roll folder, this endless belt is applied line pressure, load concentrates on regional area, so the weather resistance of endless belt has problem.When endless belt setting has the layer of oilness, skid between endless belt and the driving roll, can't transmit enough power.
When endless belt was driven into the action edge transmission with friction roller, the layer with oilness that is arranged on this endless belt was worn and torn by friction roller.In addition, during at endless belt processing pit or mount pin, by corresponding belt pulley (プ one リ) transferring power, be by the belt pulley part to the local applying load of this endless belt, so the weather resistance of endless belt has problem.
A pair of endless belt 84 with the two ends of 83 contacted of moulds, tension force transfer part 85 is set with striding complete cycle, the complete cycle ground that can stride thus band disperses tension force, can not apply large load in the local part of endless belt 84, can transmit necessary power.
When a pair of endless belt 84 arranges tension force transfer part 85, as shown in figure 10, preferably be provided for groove 83G that power transfering part 85 is passed through at metal block 83a, 83b.
As tension force transfer part 85, preferably as with the roller chain of auxiliary equipment, but the fixing parts of complete cycle of the strong transannular band 84 of tensile strength.Can be via tension force transfer part 85 with power by drive unit 86 to a pair of endless belt transmission.Drive unit 86 can use the device corresponding with tension force transfer part 85, when adopting above-mentioned roller chain, can use corresponding whelp.
According to above-mentioned the 2nd forming method, the thickness calibration deviation that can obtain length direction is the porous carbon sheet of 1.0～5.0 μ m.If standard deviation is 1.0～5.0 μ m, then as described later, can obtain the much higher hole of thickness and precision carbon plate.
The long length that refers to be difficult to by the precursor fiber sheet that intermittence, press obtained.Refer to that specifically length is more than the 10m.Consider that continuous burnt obtains porous carbon sheet and gained porous carbon sheet in the senior processibility of lower procedure, the length of precursor fiber sheet is preferably more than the 100m.The length of porous carbon sheet is preferably below the 1000m, and this can prevent that its winding diameter is excessive, operational difficulty.
The width of porous carbon sheet is preferably 10～200cm.If the width of porous carbon sheet is less than 10cm, then the aftermentioned polymer electrolyte fuel cell is difficult to obtain the gas diffuser of necessary size.For the width that the obtains porous carbon sheet sheet greater than 200cm, when carrying out described later burning till, must adopt the wide continuous furnace of stove, equipment scale is larger.
The thickness calibration deviation of porous carbon sheet length direction of the present invention is preferably 1.0～4.5 μ m.
The thickness of porous carbon sheet has very large dependency with the thickness that burns till front precursor fiber sheet.Be the precursor fiber sheet continuous burnt of 1.0～5.0 μ m by the thickness calibration deviation with length direction, the thickness calibration deviation that can obtain length direction is the porous carbon sheet of 1.0～4.5 μ m.
Porous carbon sheet of the present invention is preferably used as the gas diffuser of polymer electrolyte fuel cell.Usually, polymer electrolyte fuel cell seals supply gas with packing ring.But if the thickness deviation of gas diffuser is large, the part sealing that then thickness is large is not enough, leaks gas.In the little part of thickness, can't fully guarantee electrically contacting of the gentle bulk diffusion body of barrier film, so ohmic loss increases the problem that has battery performance to reduce.Porous carbon sheet of the present invention thickness calibration deviation in the longitudinal direction is below the 4.5 μ m, therefore the problems referred to above can not occur.
According to above-mentioned the 2nd forming method, under the state that always keeps certain intervals, heat, make thermosetting resin curedly, bonding carbon chopped fiber burns till and obtains the precursor fiber sheet of gained.Therefore, in the porous carbon sheet of the present invention 11 that obtains by above-mentioned the 2nd forming method, the abundant bonding carbon chopped fiber of resin carbonation thing, so the compress variation of thickness direction is little, the ratio resistance of thickness direction is also little.
In the above-mentioned molding procedure 23, thermosetting resin is preferably 1～3 with respect to the weight ratio of carbon chopped fiber.Thermosetting resin with respect to the weight ratio of carbon chopped fiber less than 1 o'clock, the adhesive spots reduced number of the bonding carbon chopped fiber of resin carbonation thing of porous carbon sheet, so the compressed residual deflection of the volume specific resistance of the thickness direction of this sheet and thickness direction increases.Greater than 3 o'clock, then filled up by the resin carbonation thing by the space of porous carbon sheet with respect to the weight ratio of carbon chopped fiber for thermosetting resin, and the air permeance resistance of the thickness direction of this sheet increases.
Above-mentioned interval preferably sets to such an extent that make in the above-mentioned molding procedure 23, and in the resulting precursor fiber sheet, carbon chopped fiber was with 0.05～0.27g/cm after hot briquetting was processed
3Density be included in the precursor fiber sheet, thermosetting resin is with 0.15～0.40g/cm
3Density be included in the precursor fiber sheet.As concrete interval, be 100～500 μ m with respect to 1 precursor fiber sheet preferably, more preferably 150～400 μ m, more preferably 200～350 μ m.
The fiber diameter of carbon chopped fiber changes in carbonation process 24 hardly, for the fiber diameter that makes the carbon chopped fiber that consists of porous carbon sheet is 5～20 μ m, the fiber diameter of employed carbon chopped fiber is preferably 5～20 μ m in machine hand's order 21.
Above-mentioned precursor fiber sheet preferably contains the carbonaceous powder.Specifically, as previously mentioned, in above-mentioned resin impregnated operation 22, can adopt the method for adding the carbonaceous powder in the thermosetting resin solution.Above-mentioned precursor fiber sheet is by containing the carbonaceous powder, and then not only the electroconductibility of porous carbon sheet itself improves, and in carbonation process 24 described later, when particularly using continuous furnace, can alleviate the crackle of resin carbonation thing, and the electroconductibility that can suppress sheet reduces.
In the above-mentioned carbonation process 24, can use batch kiln, but consider from productive angle, preferred one side is advanced above-mentioned precursor fiber sheet continuously in the process furnace that keeps inert atmosphere, on one side with 100～10, the heat-up rate of 000 ℃ of/minute scope is warming up to 1 at least, 200 ℃, burn till above-mentioned precursor fiber sheet, with above-mentioned thermosetting resin carbonization, then the gained porous carbon sheet is rolled into the continous way manufacturing process of web-like.
Heat-up rate in the carbonation process 24 is more preferably 300～7,000 ℃/minute scope, further preferred 500～5,000 ℃/minute.Heat-up rate is excessively slow, and then the productivity of porous carbon sheet reduces.Heat-up rate is too fast, then because the rapid Carbonization contract of thermosetting resin makes resin carbonation deposits yields crackle, make carbon chopped fiber and resin carbonation thing bonding interface peel off increase so the increase of the volume specific resistance of the thickness direction of porous carbon sheet.
Heating temperature in the above-mentioned carbonation process 24 is preferably more than 1,500 ℃, more preferably more than 1,800 ℃.Heating temperature is crossed low then has a lot of impurity residual in the porous carbon sheet, and the proton conduction that above-mentioned porous carbon sheet can be hindered solid polyelectrolyte membrane during as the gas diffuser of fuel cell reduces battery performance.Consider from the weather resistance of process furnace, catabiotic angle, Heating temperature is preferably below 2,500 ℃, more preferably below 2,200 ℃, more preferably below 2,000 ℃.
In the above-mentioned carbonation process 24, preferably in above-mentioned process furnace, be provided for making the along its length limit curved edges bending part of advancing of above-mentioned precursor fiber sheet, advance Yi Bian this precursor fiber sheet contacts with this bending part on one side.
Can make above-mentioned precursor fiber sheet crooked along its length by bending part, and so that be difficult to bending on the width, therefore, be difficult to occur in the firing process because the gauffer of the porous carbon sheet that the Carbonization contract of thermosetting resin etc. cause.And, contact with bending part by making above-mentioned, can in firing process, stretch above-mentioned, be difficult to produce gauffer, concavo-convex.
In the firing process, if the tension force of precursor fiber sheet direct of travel increases, then easily produce gauffer on the width of this sheet, if the tension force of the direct of travel of this sheet reduces, then this sheet easily produces does not have the concavo-convex of directivity.But, by using above-mentioned bending part, even the direct of travel tension force height of precursor fiber sheet also can suppress the gauffer of this sheet width, can apply high tensile to above-mentioned precursor fiber sheet.Therefore can prevent that low-tension from producing concavo-convex.
It can be 400～2,700 ℃ process furnace with Temperature Setting in the stove that above-mentioned process furnace is preferably, the process furnace that further preferably has 400～800 ℃ of temperature provinces and 1,600～2,700 ℃ of temperature provinces.Above-mentioned two kinds of temperature provinces (400～800 ℃ of temperature provinces and 1,600～2,700 ℃ of temperature provinces) can be arranged in the process furnace, process furnace can also be divided into a plurality of independently process furnace that contain corresponding to each temperature province and arrange, will burn till in two stages and carry out.To burn till and be divided into for two stages when carrying out, the sheet that the fs burns till in complete sheet, the subordinate phase sintering process all can be described as the precursor fiber sheet.
Described process furnace is that the precursor fiber sheet is advanced in being set as the space of specified temperature continuously, carries out thus the thermal treatment of precursor fiber sheet, finally makes porous carbon sheet.As the method that described (precursor fiber sheet or porous carbon sheet) advanced, to be imported in the stove by the peristome of the outer precursor fiber sheet that transmits of stove by the inlet portion of stove, heat-treat in space in specified temperature, gained sheet (precursor fiber sheet or porous carbon sheet) is derived by the peristome of the export department of stove, outside stove, batch, the method as the transmission that can easily carry out precursor fiber sheet or porous carbon sheet, advance, can make long porous carbon sheet method preferred.Oxidation (preventing uncontrolled reaction) in order to prevent the precursor fiber sheet preferably remains inert atmosphere in the stove.
A process furnace is divided into 400～800 ℃ temperature province and 1,600～2,700 ℃ temperature province, 400～800 ℃ process furnace and 1 perhaps is set, two process furnace of 600～2,700 ℃, minute 2 stages, the temperature in each temperature province (or each process furnace) respectively preferred top temperature was about 600～800 ℃ and top temperature 1 when burning till, about 600～2,700 ℃.Carrying out above-mentioned 2 stages burns till, the then thermal treatment by producing 600～800 ℃ of top temperatures that more decomposition gas, carbonization shrink and easily produce gauffer, concavo-convex etc. top temperature 1 at processed, 600～2,700 ℃ thermal treatment can change the tension force condition.
By be arranged at process furnace in bending part contact, the precursor fiber sheet is 400～2,500 ℃ crooked along its length.Described bending part is located between furnace bottom, furnace roof or furnace bottom and the furnace roof, and the whole width of preferred sheet contacts with bending part.The material that consists of described bending part can use carbon, metal, pottery, considers from cheap angle, and preferred carbon, metal when using more than 1,000 ℃, are considered particularly preferably carbon from chemical stability.
Use described bending part, observe the case of bending when precursor fiber sheet edge length direction curved edges is advanced from the side parallel with direct of travel, situation is shown in Figure 12,13 and 14.Among Figure 12, the top of following and bending part 112 of the precursor fiber sheet 111 of advancing advanced contiguously.The profile of the cross section of described bending part 112 may not be circular, but in order to prevent that sheet 111 is by with more anxious angular bend, for example as shown in Figure 3, preferably make all or part of of the face that contacts with precursor fiber sheet 121 on bending part 122 surfaces for mild curved surface.Consist of in the parts of bending part, the parts that contact with the precursor fiber sheet can rotate, and also can not rotate, and simplify the fixed sturcture that preferred employing can not be rotated in order to make block construction.
Here, length direction refers to the long side direction of precursor fiber sheet, i.e. its direct of travel.Preferred 1～10 time of the number of bends of precursor fiber sheet, more preferably 3～8 times, particularly preferably 5～7 times.Number of bends is too much, then particularly produces the gauffer of length direction when the precursor fiber sheet is heat-treated.The number of bends of 112 pairs of precursor fiber sheets 111 of 1 bending part shown in Figure 12 is 1 time, the number of bends of 122 pairs of precursor fiber sheets 121 of 3 bending parts shown in Figure 13 is 3 times, and the number of bends of 132 pairs of precursor fiber sheets 131 of 3 bending parts shown in Figure 14 is 3 times.The number of bends of precursor fiber sheet is for repeatedly the time, and at least 1 bending is carried out in the said temperature zone, and this can make the characteristic value of porous carbon sheet of the present invention suitably improve, and is therefore preferred.
In the thermal treatment zone that temperature is 400～800 ℃, therefore contained organism generation thermolysis, carbonization in the precursor fiber sheet, by making the precursor fiber bending tablet at 400～800 ℃, preferred 500～700 ℃ temperature province, can prevent gauffer.
Temperature is in the thermal treatment zone more than 1,600 ℃, can observe tension force and cause the precursor fiber sheet to produce gauffer, and this is because carbon material easily is out of shape.Surpass in 2,700 ℃ the high-temperature heat treatment zone, the consumption that consists of the carbon material of stove increases.Therefore, in temperature 1,600～2,700 ℃, preferred 1,700～2,200 ℃, more preferably make the precursor fiber bending tablet in 1,750～2,000 ℃ the thermal treatment zone, this is to prevent gauffer or concavo-convex effective means in the manufacturing of porous carbon sheet of the present invention.
But not necessarily the whole thermal treatment zone at process furnace make the precursor fiber bending tablet, can be by making the precursor fiber bending tablet prevent gauffer or concavo-convex in a part of thermal treatment zone.
The angle of bend of precursor fiber sheet be join at the precursor fiber sheet direct of travel of the position that the precursor fiber sheet of advancing and bending part join with bending part and crooked after the direct of travel angulation of precursor fiber sheet when leaving from bending part.Angle of bend is if to advance then be 0 °, for the U-shaped turnover then is 180 °, with the absolute value representation of 0～180 ° of scope.Number of bends is for repeatedly the time, and preferred at least 1 bending is to carry out in the thermal treatment zone of above-mentioned specific temperature province and with the angle of bend of specified range.Particularly preferably in temperature 1,600～2,700 ℃, preferred 1,700～2,200 ℃, more preferably bending in 1,750～2,000 ℃ the thermal treatment zone all is below the higher limit of the interior angle of bend of specified range and more than the lower value.Figure 15 is the side schematic view of explanation angle of bend.
Among Figure 15, the direct of travel of the precursor fiber sheet 141 of the position that will join with bending part 142 prolongs, and dots, and this dotted line is angle of bend with direct of travel angulation 143 from the precursor fiber sheet 141 of the position that bending part 142 leaves.Preferred 3～180 ° of angle of bend, more preferably 5～25 °, particularly preferably 6～10 °.Angle of bend hour prevents that by bending the effect of gauffer is insufficient.When calculating angle of bend, need not to consider the sagging of precursor fiber sheet that gravity etc. causes, can be calculated by the configuration of bending part.When angle of bend was large, the height of stove was high, kept the energy expenditure of temperature in the stove to increase.
When the precursor fiber sheet contains the organism of non-fiber, if increase angle of bend then have the trend that crackle or direct of travel produce gauffer appears on the precursor fiber sheet.For preventing these problems, angle of bend is preferably 5～25 °, more preferably 6～10 °.As the organism of non-fiber, crackle, gauffer occur easily when containing resol, furane resin, melamine resin, pitch particularly, therefore, preferred 5～25 ° of angle of bend, further preferred 6～10 °.And by copying the paper legal system when making the precursor fiber sheet, interfibrous entanglement is few, easily split, so preferred 5～25 ° of angle of bend, further preferred 6～10 °.
Equally, when but the precursor fiber sheet contains the organism of carbonization of carbon chopped fiber and bonding this carbon chopped fiber, when perhaps the precursor fiber sheet contains the organic carbide of carbon chopped fiber and bonding carbon chopped fiber, if angle of bend increases, then there is this precursor fiber sheet the tendency of crackle or direct of travel generation gauffer to occur.For preventing these problems, preferred 5～25 ° of angle of bend, more preferably 6～10 °.But the organism of carbonization is to be approximately the following organism of 90wt% at loss of weight under the inert atmospheres such as nitrogen, when heat-treating with 1,000 ℃ of top temperature, and resol, furane resin, melamine resin, pitch are for example arranged.Particularly by copying the paper legal system when making the precursor fiber sheet, interfibrous entanglement is few, easily cracks, and therefore preferred angle of bend is 5～25 °, further preferred 6～10 °.
In the manufacture method of porous carbon sheet of the present invention, make precursor fiber sheet and first bending part upper face side, then contact successively with the following side of bending part, two sides in the table of this precursor fiber sheet is crooked successively, can improve thus the contact pressure of precursor fiber sheet and bending part, increase number of bends, prevent gauffer.
Figure 14 is the side schematic view of an expression one example.Among Figure 14, the following side contacts of the 1st bending part 132a in the surface of the precursor fiber sheet 131 of advancing and three bending parts 132, be bent, then, the inside of precursor fiber sheet 131 contacts with the upper face side of the 2nd bending part 132b, is bent, and follows again, the following side contacts of the surface of precursor fiber sheet 131 and the 3rd bending part 132c is bent again.Can consider the position of furnace bottom and furnace roof to be arranged in the stove with the bending part that two sides in the table of precursor fiber sheet contacts successively.
In the manufacture method of porous carbon sheet of the present invention, in the furnace outlet part, the tension force that precursor fiber sheet or porous carbon sheet are applied is preferably 3～100N/m, more preferably 5～50N/m, particularly preferably 10～25N/m.Tension force is crossed when low, can't be prevented gauffer, prevent concavo-convex effect, the trend that then has the width of sheet fracture or sheet to shrink when tension force is too high.The tension force that puts on sheet can be controlled by the speed of drawing in the process furnace by speed and the sheet of precursor fiber sheet supply process furnace.
In the manufacture method of porous carbon sheet of the present invention, can the precursor fiber sheet more than 2 is spaced apart parallel up and down, supply with simultaneously process furnace.Precursor fiber sheet more than 2 can also be supplied with process furnace abreast simultaneously about on the direction of vertical direct of travel.Aforesaid method can improve the manufacturing efficient of porous carbon sheet.But for they are carried out uniform thermal treatment, the sheet number of the precursor fiber sheet being supplied with simultaneously process furnace is preferably below 5.
In the manufacture method of porous carbon sheet of the present invention, to having temperature 1, more than 600 ℃ the process furnace of thermal treatment zone advance and the precursor fiber sheet supplied with to be peristome by the entrance of this process furnace import in the stove, heat-treat in warmed-up space, then derived by the peristome of the outlet of this process furnace, make porous carbon sheet.The porous carbon sheet of preferably being derived, being advanced by this process furnace is rolled into web-like by being located at the outer sheet spooler of this process furnace.
Bending part preferably is set in this process furnace, and this bending part contacts with the two sides of the precursor fiber sheet of advancing under the temperature more than 1,600 ℃.By this bending part, can prevent the gauffer that produces at porous carbon sheet or concavo-convex.Bending part can be located at at the end, top or end and top of process furnace.Bending part preferably comprises the rhoptry of being located at the direction that the direct of travel with sheet intersects, and this can make it contact with the whole width of sheet, according to circumstances also can be tabular body.
The long limit that rhoptry refers to its cross section with the ratio of minor face at 4 times with interior rhoptry.By using rhoptry, can reduce the height of bending part.Can also shorten the contact length with sheet, prevent the wearing and tearing of the sheet that contacts.The preferred price of rhoptry is low, chemically stable carbonaceous in inert atmosphere.
Process furnace with temperature thermal treatment zone more than 1,600 ℃, the height between its furnace bottom and the furnace roof can be 20～300mm, preferred 60～200mm.This highly represents the height that sheet can pass through.The stove inner height is excessively low, then in order to prevent that crooked contact furnace roof or furnace bottom from must reduce contact angle, increases the number of bending part, continually alternating bending.The energy waste that the heat release of the too high then stove of stove inner height causes increases.
When use comprises the claval bending part of carbon, for preventing the overbending of sheet, prevent the wearing and tearing of bending part, contain for example as shown in figure 14 bending part 132 of the claval bending part of carbon, preferably its surface and contacted of sheet all or part of by Machining of Curved Surface.Comprise the claval bending part (hereinafter referred to as horizontal bar) that is disposed at the direction that the side of advancing with sheet intersects and preferably in stove, arrange 1～10, more preferably arrange 3～8, further preferably arrange 5～7.Horizontal bar can be to be installed in independently more than 1 in the stove, perhaps with biside plate and horizontal bar combination, with the shape configuration of ladder shape.
Jut preferably is set respectively on a plurality of horizontal bars, interconnects by jut and be integral.By integrated, can be with a plurality of horizontal bars as a body component, then can easily carry out inserting in fixing in the stove, the stove, take out in the stove, mobile in the stove.
Figure 16 represents that 3 horizontal bars 151 are fixed on the side schematic view of formed ladder sigmoid parts on biside plate (the two perpendicular rods) 152.Figure 17 is the cross section that has identical shaped horizontal bar 161 with the horizontal bar 151 of Figure 16.When the bending part of ladder shape shown in Figure 16 was placed on furnace bottom, following and the furnace bottom of side plate (perpendicular rod) 152 contacted, and can produce the slit at the downside of horizontal bar 151, so can make sheet alternatively by getting off to advance on the horizontal bar 151.
By selecting the shape of bending part, even under process furnace is heated to state more than 1,600 ℃, also can only bending part be taken out or put into stove in stove, therefore need not cooling or stopped heating stove and namely can change bending part.
Bending part in stove setting or change and for example can followingly carry out: for bending part is inserted in the stove, is moved to and be heated to 1 by stove entrance or outlet of still, zone more than 600 ℃, and for bending part from being heated to 1, shift out in zone more than 600 ℃, take out from stove entrance or outlet of still, can baffle plate to be opened/closed (shutter) be set at stove entrance or outlet of still.For the end along process furnace is slided bending part, furnace bottom is preferably smooth.The transport unit such as band, chain that is preferred for transmitting bending part is installed in the process furnace.
Among the following embodiment, definition and/or the measuring method of each characteristic value of porous carbon sheet are as described below.
Thickness after precursor fiber sheet and this sheet moulding:
Same with the measuring method of the thickness of above-mentioned porous carbon sheet.
The thickness calibration deviation of precursor fiber leaf length direction after the molding procedure:
The thickness calibration deviation of precursor fiber leaf length direction is calculated with the thickness data more than measuring space 100 places of 5cm along the length direction of this sheet after the molding procedure.The measuring method of thickness as mentioned above.
The thickness calibration deviation of the length direction of porous carbon sheet:
The thickness calibration deviation of porous carbon sheet length direction according to above-mentioned molding procedure after the same method of precursor fiber sheet calculate.
The depth of camber of porous carbon sheet:
Be that the square Porous carbon fiber sheet of 200mm is tabular and places with the length of side that cuts, if gauffer is arranged or when concavo-convex, then this sheet warpage produces high part.The height of the extreme higher position of the depth of camber of porous carbon sheet by measuring this sheet calculates.
Embodiment 1
It is long that carbonized polyacrylonitrile fibre " ト レ カ (the registered trademark) " T300-6K (average single fiber diameter: 7 μ m, single fiber dimension: 6,000) that eastern レ Co., Ltd. is made is cut into 12mm, obtains carbon chopped fiber., as the medium of manufacturing paper with pulp this carbon chopped fiber is manufactured paper with pulp continuously with water.The carbon fiber paper of manufacturing paper with pulp further is immersed in the 10 % by weight aqueous solution of polyvinyl alcohol, drying, the weight per unit area that obtains carbon chopped fiber is about 22g/m
2Long carbon fiber paper, be rolled into web-like.With respect to 100 weight part carbon fiber papers, the adhesion amount of polyvinyl alcohol is equivalent to 20 weight parts.
With in more flaky graphite BF-5A (median size 5 μ m), resol and the methyl alcohol of blacklead industry manufacturing are mixed to get dispersion liquid according to 1: 5: 24 weight ratio.Make the continuously above-mentioned dispersion liquid of impregnation of above-mentioned carbon fiber paper, so that with respect to 100 weight part carbon chopped fibers, resol is 192 weight parts, drying is 3 minutes under 90 ℃ temperature, obtains containing the carbon fiber paper of resin pickup, is rolled into web-like.Resol is to use the resin that resole (レ ゾ one Le type Off エ ノ one Le Trees fat) and varnish-type phenolic resin (ノ ボ ラ Star Network type Off エ ノ one Le Trees fat) are mixed to get according to 1: 1 weight ratio.
On the 100t press that カ ワ ジ リ company of Co., Ltd. makes, hot plate 33,34 is installed parallel to each other, configuration space body 35,35 on lower hot plate 34, press under the 0.8MPa repeatedly folding of press at 170 ℃ of hot plate temperatures, face, transmit by phased manner simultaneously up and down the carbon fiber paper that contains resin pickup with the release paper clamping, be total to heating and pressurizing 6 minutes in identical position, carry out processed compressed.Remove release paper thickness, be spaced apart 0.30mm for the set essence of carbon fiber paper moulding that contains resin pickup.The effective pressurization length L P of hot plate is 1,200mm, and when transmitting by phased manner, the conveying capacity LF of precursor fiber sheet is 100mm, LF/LP=0.08.That is, send into (100mm) by the heating and pressurizing, die sinking, the carbon fiber paper that repeatedly carried out 30 seconds and carry out processed compressed, be rolled into web-like.
To carry out the above-mentioned carbon fiber paper of processed compressed as the precursor fiber sheet, import to that to keep nitrogen atmosphere, top temperature be 2, in 000 ℃ the process furnace, in process furnace, advance continuously, simultaneously with approximately 500 ℃/minute (to 650 ℃ with 400 ℃/minute, surpass 650 ℃ temperature with 550 ℃/minute) heat-up rate burn till, be rolled into web-like.The various physical property of gained porous carbon sheet 11, create conditions and evaluation result as follows.The micropore diameter measure of spread result that porous carbon sheet 11 is undertaken by mercury penetration method as shown in Figure 1.
Micropore mould footpath: 58 μ m
Differential pressure 6mmAq/mm when through-thickness sees through air
The volume specific resistance of thickness direction: 130m Ω cm
The residual set amount of through-thickness compression: 6 μ m
The thickness calibration deviation of length direction: 6.5 μ m
Depth of camber: 4.5mm
Density: 0.24g/cm
3
Thickness: 0.20mm
Weight per unit area: 48g/m
2
The weight per unit area of carbon chopped fiber: 22g/m
2
The weight per unit area of thermosetting resin: 42g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 1.9
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.40mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.32mm
The density of carbon chopped fiber: 0.07g/cm after the molding procedure
3
The density of thermosetting resin: 0.13g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 10.4 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Embodiment 2
The weight per unit area that makes the middle carbon chopped fiber of manufacturing paper with pulp is 18g/m
2, with respect to 100 weight part carbon chopped fibers, making resol is that 276 weight part ground contain resin pickup, in addition obtains similarly to Example 1 porous carbon sheet 11.The various characteristics of the porous carbon sheet 11 of gained, create conditions and evaluation result as follows.
Micropore mould footpath: 65 μ m
Differential pressure when through-thickness sees through air: 5mmAq/mm
The volume specific resistance of thickness direction: 110m Ω cm
The residual set amount of through-thickness compression: 7 μ m
The thickness calibration deviation of length direction: 6.8 μ m
Depth of camber: 4.3mm
Density: 0.25g/cm
3
Thickness: 0.20mm
Weight per unit area: 50g/m
2
The weight per unit area of carbon chopped fiber: 18g/m
2
The weight per unit area of thermosetting resin: 48g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 2.7
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.39mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.31mm
The density of carbon chopped fiber: 0.06g/cm after the molding procedure
3
The density of thermosetting resin: 0.15g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 10.5 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Embodiment 3
The weight per unit area that makes the middle carbon chopped fiber of manufacturing paper with pulp is 26g/m
2, with respect to 100 weight part carbon chopped fibers, making resol is that 175 weight part ground contain resin pickup, in addition obtains similarly to Example 1 porous carbon sheet 11.The various characteristics of the porous carbon sheet 11 of gained, create conditions and evaluation result as follows.
Micropore mould footpath: 50 μ m
Differential pressure 9mmAq/mm when through-thickness sees through air
The volume specific resistance of thickness direction: 150m Ω cm
The residual set amount of through-thickness compression: 5 μ m
The thickness calibration deviation of length direction: 6.4 μ m
Depth of camber: 4.9mm
Density: 0.27g/cm
3
Thickness: 0.20mm
Weight per unit area: 54g/m
2
The weight per unit area of carbon chopped fiber: 26g/m
2
The weight per unit area of thermosetting resin: 46g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 1.8
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.42mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.33mm
The density of carbon chopped fiber: 0.08g/cm after the molding procedure
3
The density of thermosetting resin: 0.14g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 10.6 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Embodiment 4
It is long that carbonized polyacrylonitrile fibre " ト レ カ (the registered trademark) " T300-6K (average single fiber diameter: 7 μ m, single fiber dimension: 6,000) that eastern レ Co., Ltd. is made is cut into 12mm, obtains carbon chopped fiber.This carbon chopped fiber is manufactured paper with pulp as the medium of manufacturing paper with pulp with water.The carbon fiber paper of manufacturing paper with pulp further is immersed in the 10 % by weight aqueous liquid dispersions of polyvinyl alcohol, drying, the weight per unit area that obtains carbon chopped fiber is about 22g/m
2Carbon fiber paper.With respect to 100 weight part carbon fiber papers, the adhesion amount of polyvinyl alcohol is equivalent to 10 weight parts.
Then, 10 % by weight methanol solutions of impregnation resol in above-mentioned carbon fiber paper so that with respect to 100 weight part carbon chopped fibers, resol is 220 weight parts, 90 ℃ of dryings, obtain containing the carbon fiber paper of resin pickup thus.Resol uses resole and varnish-type phenolic resin to mix the resin of gained according to 1: 1 weight ratio.
On the 100t press that カ ワ ジ リ company of Co., Ltd. makes, hot plate is installed parallel to each other, configuration space body on hot plate, press 0.8MPa to press down (press) up and down with the above-mentioned carbon fiber paper that contains resin pickup of release paper clamping at 150 ℃ of hot plate temperatures, face, carry out 30 minutes processed compressed.For the set essence of carbon fiber paper moulding that contains resin pickup is spaced apart 0.33mm.
Then, with processed compressed above-mentioned carbon fiber paper as the precursor fiber sheet, use to keep the batch kiln of nitrogen atmosphere, burn till at 2,000 ℃.Heat-up rate be 1.4 ℃/minute (to 800 ℃ be 1 ℃/minute, the temperature that surpasses 800 ℃ is 2 ℃/minute).The various characteristics of the porous carbon sheet 11 of gained is as follows.
Micropore mould footpath: 60 μ m
Differential pressure when through-thickness sees through air: 5mmAq/mm
The volume specific resistance of thickness direction: 100m Ω cm
The residual set amount of through-thickness compression: 5 μ m
The thickness calibration deviation of length direction: 6.6 μ m
Depth of camber: 4.3mm
Density: 0.22g/cm
3
Thickness: 0.21mm
Weight per unit area: 47g/m
2
The weight per unit area of carbon chopped fiber: 22g/m
2
The weight per unit area of thermosetting resin: 48g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 2.2
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.40mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.35mm
The density of carbon chopped fiber: 0.06g/cm after the molding procedure
3
The density of thermosetting resin: 0.14g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 11.0 μ m
The heat-up rate of carbonation process: 1.4 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Embodiment 5
Except molding procedure 23, obtain similarly to Example 1 porous carbon sheet 11.Below molding procedure is described.
Similarly to Example 1, preparation contains the carbon fiber paper of resin pickup, this sheet 82 is cut into length 100m, wide 30cm, with a pair of Stainless Steel Band 84 as a pair of band clamping, the fluorine coating has been carried out by PTFE in two surfaces of this a pair of Stainless Steel Band 84, speed with 0.6m/ minute is introduced in the mould 83 with the slit that is heated to 230 ℃ of temperature continuously on one side under this clamp position, on one side carry out hot briquetting, obtain thus the precursor fiber sheet 81 after the molding procedure of length 100m, width 30cm.
Micropore mould footpath: 59 μ m
Differential pressure when through-thickness sees through air: 6mmAq/mm
The volume specific resistance of thickness direction: 120m Ω cm
The residual set amount of through-thickness compression: 4 μ m
The thickness calibration deviation of length direction: 3.4 μ m
Depth of camber: 4.5mm
Density: 0.25g/cm
3
Thickness: 0.20mm
Weight per unit area: 49g/m
2
The weight per unit area of carbon chopped fiber: 22g/m
2
The weight per unit area of thermosetting resin: 43g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 2.0
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.41mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.33mm
The density of carbon chopped fiber: 0.07g/cm after the molding procedure
3
The density of thermosetting resin: 0.13g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 5.7 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Embodiment 6
Except firing process 24, obtain similarly to Example 1 porous carbon sheet 11.Below firing process is described.
Prepare similarly to Example 1 the carbon fiber paper that contains resin pickup after the molding procedure.With this carbon fiber paper as the precursor fiber sheet, import to that to keep nitrogen atmosphere, top temperature be 2, in 000 ℃ the process furnace, in process furnace, advance continuously, simultaneously take approximately 500 ℃/minute (to 650 ℃ as 400 ℃/minute, the temperature that surpasses 650 ℃ is 550 ℃/minute) heat-up rate burn till, be rolled into web-like.
When burning till, in process furnace, the ladder sigmoid parts that furnace bottom is furnished with horizontal bar that are configured in according to Figure 14 make the precursor fiber bending tablet.The cross-sectional shape of horizontal bar is high 25mm, wide 25mm, the top and bottom ellipticity of having implemented Machining of Curved Surface (little declare shape).3 horizontal bars of bending part according to above-mentioned contacted order, be horizontal bar 132a, 132b, 132c successively, temperature is in the stove: horizontal bar 132a is disposed at 1,750 ℃ position, horizontal bar 132c and is disposed at 1950 ℃ position.Above-mentioned angle of bend is: with the contacted part of horizontal bar 132a be 7 °, the part of joining with horizontal bar 132b is 14 °, with the contacted part of horizontal bar 132c be 7 °.Each characteristic of gained porous carbon sheet 11 is as follows.
Micropore mould footpath: 58 μ m
Differential pressure when through-thickness sees through air: 6mmAq/mm
The volume specific resistance of thickness direction: 110m Ω cm
The residual set amount of through-thickness compression: 6 μ m
The thickness calibration deviation of length direction: 6.7 μ m
Depth of camber: 1.0mm
Density: 0.24g/cm
3
Thickness: 0.20mm
Weight per unit area: 48g/m
2
The weight per unit area of carbon chopped fiber: 22g/m
2
The weight per unit area of thermosetting resin: 42g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 1.9
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.40mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.32mm
The density of carbon chopped fiber: 0.07g/cm after the molding procedure
3
The density of thermosetting resin: 0.13g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 10.8 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Embodiment 7
Except firing process 24, obtain similarly to Example 5 porous carbon sheet 11.Below firing process is described.
Prepare similarly to Example 5 the carbon fiber paper that contains resin pickup after the molding procedure.With this carbon fiber paper as the precursor fiber sheet, import to that to keep nitrogen atmosphere, top temperature be 2, in 000 ℃ the process furnace, in process furnace, advance continuously, simultaneously take approximately 500 ℃/minute (to 650 ℃ as 400 ℃/minute, the temperature that surpasses 650 ℃ is with 550 ℃/minute) heat-up rate burn till, be rolled into web-like.
When burning till, in the process furnace, according to the configuration of Figure 14, be furnished with the ladder sigmoid parts of horizontal bar at furnace bottom, make bending tablet.The cross-sectional shape of horizontal bar is high 25mm, wide 25mm, and as shown in figure 17, the lower, outer perimeter line has respectively the curve of convex to foreign side, and the lower end about the lower end about upper outer peripheral line and lower outer peripheral line connects with straight line.Three horizontal bars of bending part and the engagement sequence of sheet are 132a, 132b, 132c successively, and temperature is that horizontal bar 132a is disposed at 1750 ℃ position in the stove, and horizontal bar 132c is disposed at 1950 ℃ position.Above-mentioned angle of bend is that the part that contacts with horizontal bar 132a is 7 °, and the part that contacts with horizontal bar 132b is 14 °, and the part that contacts with horizontal bar 132c is 7 °.The various characteristics of gained porous carbon sheet 11 is as follows.
Micropore mould footpath: 57 μ m
Differential pressure when through-thickness sees through air: 6mmAq/mm
The volume specific resistance of thickness direction: 110m Ω cm
The residual set amount of through-thickness compression: 4 μ m
The thickness calibration deviation of length direction: 3.5 μ m
Depth of camber: 0.9mm
Density: 0.24g/cm
3
Thickness: 0.20mm
Weight per unit area: 48g/m
2
The weight per unit area of carbon chopped fiber: 22g/m
2
The weight per unit area of thermosetting resin: 42g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 1.9
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.40mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.32mm
The density of carbon chopped fiber: 0.07g/cm after the molding procedure
3
The density of thermosetting resin: 0.13g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 5.6 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Comparative example 1
It is long that carbonized polyacrylonitrile fibre " ト レ カ (the registered trademark) " T300-6K (average single fiber diameter: 7 μ m, single fiber dimension: 6,000) that eastern レ Co., Ltd. is made is cut into 12mm, obtains carbon chopped fiber.This carbon chopped fiber is manufactured paper with pulp as the medium of manufacturing paper with pulp continuously with water.The carbon fiber paper of manufacturing paper with pulp further is immersed in the 10 % by weight aqueous solution of polyvinyl alcohol, drying, the weight per unit area that obtains carbon chopped fiber is about 14g/m
2Long carbon fiber paper, be rolled into web-like.With respect to 100 weight part carbon fiber papers, the adhesion amount of polyvinyl alcohol is equivalent to 20 weight parts.
With in more flaky graphite BF-5A (median size 5 μ m), resol and the methyl alcohol of blacklead industry manufacturing are mixed to get dispersion liquid according to 1: 1: 8 weight ratio.Make the continuously above-mentioned dispersion liquid of impregnation of above-mentioned carbon fiber paper, so that with respect to 100 weight part carbon chopped fibers, resol is 158 weight parts, dry 3 minutes of 90 ℃ temperature, obtain thus containing the carbon fiber paper of resin pickup, be rolled into web-like.Resol is to use the resin that resole and varnish-type phenolic resin are mixed to get according to 1: 1 weight ratio.
With the heating 6 minutes in being set as 170 ℃ baking oven of the above-mentioned carbon fiber paper that contains resin pickup, heat-treat.
Will be through the above-mentioned carbon fiber paper of heat treated as the precursor fiber sheet, import to that to keep nitrogen atmosphere, top temperature be 2, in 000 ℃ the process furnace, in process furnace, advance continuously, simultaneously take approximately 500 ℃/minute (to 650 ℃ as 400 ℃/minute, the temperature that surpasses 650 ℃ is with 550 ℃/minute) heat-up rate burn till, be rolled into web-like.The various characteristics of gained porous carbon sheet, create conditions and evaluation result as follows.
Micropore mould footpath: 93 μ m
Differential pressure when through-thickness sees through air: 6mmAq/mm
The volume specific resistance of thickness direction: 100m Ω cm
The residual set amount of through-thickness compression: 32 μ m
The thickness calibration deviation of length direction: 8.4 μ m
Depth of camber: 4.5mm
Density: 0.21g/cm
3
Thickness: 0.21mm
Weight per unit area: 44g/m
2
The weight per unit area of carbon chopped fiber: 14g/m
2
The weight per unit area of thermosetting resin: 22g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 1.6
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.35mm
The thickness that contains the carbon fiber paper of resin pickup after the thermal treatment: 0.34mm
The density of carbon chopped fiber: 0.04g/cm after the thermal treatment
3
The density of thermosetting resin: 0.06g/cm after the thermal treatment
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 13.7 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Comparative example 2
With respect to 100 weight part carbon chopped fibers, making resol is that 221 weight part ground contain resin pickup, in addition similarly obtains porous carbon sheet with comparative example 1.The various characteristics of gained porous carbon sheet, create conditions and evaluation result as follows.
Micropore mould footpath: 91 μ m
Differential pressure when through-thickness sees through air: 14mmAq/mm
The volume specific resistance of thickness direction: 80m Ω cm
The residual set amount of through-thickness compression: 21 μ m
The thickness calibration deviation of length direction: 8.8 μ m
Depth of camber: 4.2mm
Density: 0.27g/cm
3
Thickness: 0.22mm
Weight per unit area: 59g/m
2
The weight per unit area of carbon chopped fiber: 14g/m
2
The weight per unit area of thermosetting resin: 31g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 2.2
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.36mm
The thickness that contains the carbon fiber paper of resin pickup after the thermal treatment: 0.34mm
The density of carbon chopped fiber: 0.04g/cm after the thermal treatment
3
The density of thermosetting resin: 0.09g/cm after the thermal treatment
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 13.4 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Comparative example 3
It is long that carbonized polyacrylonitrile fibre " ト レ カ (the registered trademark) " T300-6K (average single fiber diameter: 7 μ m, single fiber dimension: 6,000) that eastern レ Co., Ltd. is made is cut into 12mm, obtains carbon chopped fiber.This carbon chopped fiber is manufactured paper with pulp as the medium of manufacturing paper with pulp with water.The carbon fiber paper of manufacturing paper with pulp further is immersed in the 20 % by weight aqueous liquid dispersions of polyvinyl alcohol, drying, the weight per unit area that obtains carbon chopped fiber is about 25g/m
2Carbon fiber paper.With respect to 100 weight part carbon fiber papers, the adhesion amount of polyvinyl alcohol is equivalent to 10 weight parts.
Then, 10 % by weight methanol solutions of impregnation resol in above-mentioned carbon fiber paper so that with respect to 100 weight part carbon chopped fibers, resol is 69 weight parts, 90 ℃ of lower dryings, obtain containing the carbon fiber paper of resin pickup thus.Resol uses resole and varnish-type phenolic resin to mix the resin of gained according to 1: 1 weight ratio.
On the 100t press that カ ワ ジ リ company of Co., Ltd. makes, hot plate is installed parallel to each other, 150 ℃ of hot plate temperatures, face press 0.5MPa press down up and down with the release paper clamping, 2 above-mentioned stacked gained multilayer body of carbon fiber paper that contain resin pickup, carry out 30 minutes processed compressed.
Then, the above-mentioned carbon fiber paper of compressed processing as the precursor fiber sheet, is used the batch kiln that keeps nitrogen atmosphere, burn till at 2,000 ℃.Heat-up rate be 1.4 ℃/minute (to 800 ℃ be 1 ℃/minute, the temperature that surpasses 800 ℃ is 2 ℃/minute).The various characteristics of the porous carbon sheet of gained is as follows.
Micropore mould footpath: 39 μ m
Differential pressure 13mmAq/mm when through-thickness sees through air
The volume specific resistance of thickness direction: 150m Ω cm
The residual set amount of through-thickness compression: 10 μ m
The thickness calibration deviation of length direction: 6.4 μ m
Depth of camber: 4.9mm
Density: 0.30g/cm
3
Thickness: 0.22mm
Weight per unit area: 66g/m
2
The weight per unit area of carbon chopped fiber: 50g/m
2(2)
The weight per unit area of thermosetting resin: 35g/m
2(2)
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 0.7
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.80mm (2)
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.25mm
The density of carbon chopped fiber: 0.20g/cm after the molding procedure
3
The density of thermosetting resin: 0.14g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 7.4 μ m
The heat-up rate of carbonation process: 1.4 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Comparative example 4
Making resol with respect to 100 weight part carbon chopped fibers is that 49 weight part ground contain resin pickup, in addition similarly obtains porous carbon sheet with comparative example 3.The various characteristics of the porous carbon sheet of gained, create conditions and evaluation result as follows.
Micropore mould footpath: 41 μ m
Differential pressure when through-thickness sees through air: 7mmAq/mm
The volume specific resistance of thickness direction: 550m Ω cm
The residual set amount of through-thickness compression: 12 μ m
The thickness calibration deviation of length direction: 6.8 μ m
Depth of camber: 4.7mm
Density: 0.25g/cm
3
Thickness: 0.24mm
Weight per unit area: 61g/m
2
The weight per unit area of carbon chopped fiber: 50g/m
2(2)
The weight per unit area of thermosetting resin: 25g/m
2(2)
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 0.5
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.80mm (2)
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.27mm
The density of carbon chopped fiber: 0.19g/cm after the molding procedure
3
The density of thermosetting resin: 0.09g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 7.7 μ m
The heat-up rate of carbonation process: 1.4 ℃/minute
The top temperature of carbonation process: 2,000 ℃
Comparative example 5
In compression section 23, on hot plate, do not configure interval body, the face of press is pressed as 0.1MPa, in addition obtain similarly to Example 1 porous carbon sheet.The various characteristics of gained porous carbon sheet, create conditions and evaluation result as follows.
Micropore mould footpath: 38 μ m
Differential pressure when through-thickness sees through air: 25mmAq/mm
The volume specific resistance of thickness direction: 70m Ω cm
The residual set amount of through-thickness compression: 7 μ m
The thickness calibration deviation of length direction: 3.5 μ m
Depth of camber: 5.2mm
Density: 0.44g/cm
3
Thickness: 0.11mm
Weight per unit area: 48g/m
2
The weight per unit area of carbon chopped fiber: 22g/m
2
The weight per unit area of thermosetting resin: 42g/m
2
Thermosetting resin is with respect to the weight ratio of carbon chopped fiber: 1.9
The fiber diameter of carbon fiber: 7 μ m
The thickness that contains the carbon fiber paper of resin pickup: 0.40mm
The thickness that contains the carbon fiber paper of resin pickup after the molding procedure: 0.13mm
The density of carbon chopped fiber: 0.17g/cm after the molding procedure
3
The density of thermosetting resin: 0.32g/cm after the molding procedure
3
The standard deviation of precursor fiber sheet thickness direction after the molding procedure: 4.3 μ m
The heat-up rate of carbonation process: 500 ℃/minute
The top temperature of carbonation process: 2,000 ℃
For above embodiment and comparative example, the various characteristics of porous carbon sheet, create conditions and evaluation result in main contents be summarized in following table 1.
[table 1]
The porous carbon sheet 11 of above-described embodiment 1～7 is that weight per unit area take carbon chopped fiber 12 is as 15～30g/m
2, thermosetting resin weight per unit area be 30～80g/m
2, arrange in molding procedure 23 that certain intervals makes, therefore the micropore mould directly can be controlled at the proper range of 45～90 μ m.Therefore the porous carbon sheet 11 of embodiment 1～7 all is shown as sufficient value in the residual set amount of the volume specific resistance of thickness direction, through-thickness compression, each evaluation result of differential pressure when through-thickness sees through air, satisfies fully simultaneously the desired characteristic of porous carbon sheet to the cell gas diffuser material that acts as a fuel.
Embodiment 5 and 7 porous carbon sheet 11 are in molding procedure 23, and the thickness of precursor fiber sheet is controlled at the interval of the slit by being arranged at mould.Therefore, even the inhomogeneous material of applying unit area weight, the part that weight per unit area is high applies high pressure, and the part low to weight per unit area applies low pressure.Therefore, the thickness calibration deviation of embodiment 5 and 7 porous carbon sheet 11 length directions is 3.4 μ m and 3.5 μ m, has very high thickness and precision.
Embodiment 6 and 7 porous carbon sheet 11 are to use bending part in firing process 24, with precursor fiber sheet crooked make along its length.Therefore, this sheet is difficult on width crooked, therefore is difficult to produce gauffer.And, by contacting with this bending part, be difficult to produce gauffer, concavo-convex.Therefore, the depth of camber of embodiment 6 and 7 porous carbon sheet 11 is 1.0mm and 0.9mm, gauffer, concavo-convex considerably less.
Comparative example 1 and comparative example 2 are not make resin solidification with carrying out processed compressed, so the micropore mould of porous carbon sheet directly is 93 and 91 μ m, and larger, the compressed residual deflection of thickness direction is 32 and 21 μ m, and is larger.
The carbon chopped fiber weight per unit area of comparative example 3 and comparative example 4 is 50g/m
2, larger, in compression section, by interval body etc. the interval is not set, be to carry out heating and pressurizing with high press pressure to process, so the micropore mould of porous carbon sheet directly is 39 and 41 μ m, less.The weight per unit area of thermosetting resin is higher 35g/m
2Comparative example 3 in, the volume specific resistance of thickness direction is 150m Ω cm, and is lower, but the differential pressure of through-thickness when seeing through air is 14mmAq/mm, higher.Weight per unit area at thermosetting resin is higher 25g/m
2Comparative example 4 in, the differential pressure when through-thickness sees through air is 7mmAq/mm, and is higher, but the volume specific resistance of thickness direction is 550m Ω cm, lower.Therefore, micropore mould footpath hour, the differential pressure in the time of can't satisfying simultaneously through-thickness and see through air and the volume specific resistance of thickness direction.
The carbon fiber paper that contains resin pickup that comparative example 5 uses similarly to Example 1, but by interval body etc. the interval is not set, process even therefore carry out heating and pressurizing by the lower press pressure of 0.1MPa, the thickness of the carbon fiber paper that contains resin pickup behind the compression section is also thin, is 0.13mm.Therefore, can't suitably control the micropore mould footpath of porous carbon sheet, be 38 μ m, less, the volume specific resistance of thickness direction is 70m Ω cm, and is lower, but the differential pressure of through-thickness when seeing through air is 25mmAq/mm, higher.
As mentioned above, according to the manufacture method of porous carbon sheet of the present invention, can provide fully simultaneously satisfy for the porous carbon sheet of the gas diffuser material of the battery that acts as a fuel require characteristic, ventilation property is high specifically, electroconductibility is high, the little porous carbon sheet of residual set amount after the compression.
Industrial applicability
Porous carbon sheet of the present invention can satisfy the desired characteristic of carbon paper of the cell gas diffuser that acts as a fuel that in the past was difficult to satisfy fully simultaneously fully simultaneously, and ventilation property is high specifically, electroconductibility is high, the compressed residual deflection is little.
Porous carbon sheet of the present invention satisfies above-mentioned characteristic, therefore is preferably used as the gas diffuser material that automobile is used polymer electrolyte fuel cell.Porous carbon sheet of the present invention is not limited to the gas diffuser of polymer electrolyte fuel cell, also can be applied to the electrode base material of the various batteries such as direct methanol fuel cell or water extracter with electrode etc.Its purposes is not limited to these.
Take make porous carbon sheet of the present invention as the manufacture method of the porous carbon base material of the present invention of purpose be the manufacture method with porous carbon sheet of following operation: the precursor fiber sheet that will contain carbon chopped fiber and thermosetting resin carries out the molding procedure that hot briquetting is processed; Contained thermosetting resin in this precursor fiber sheet of processing through hot briquetting is carried out the carbonation process of carbonizing treatment; The method is characterized in that: in above-mentioned molding procedure, carry out the molding precursor fibre plate with the hot plate that is provided with certain intervals.According to the manufacture method of porous carbon sheet of the present invention, can make fully simultaneously to satisfy and be difficult to the porous carbon sheet that ventilation property is high, electroconductibility is high, the compressed residual deflection is little made in the past.
Claims (20)
1. prepare the manufacture method of the porous carbon sheet of porous carbon sheet, the method has following operation: the precursor fiber sheet that will contain carbon chopped fiber and thermosetting resin carries out the molding procedure that hot briquetting is processed; Will be in the precursor fiber sheet that hot briquetting is processed contained thermosetting resin carry out the carbonation process of carbonizing treatment; The method is characterized in that: be 15～30g/m at the weight per unit area with above-mentioned carbon chopped fiber
2, above-mentioned thermosetting resin weight per unit area be 30～80g/m
2Precursor fiber sheet when in above-mentioned molding procedure, carrying out moulding by the hot plate that is provided with certain intervals, set the above-mentioned interval in the above-mentioned molding procedure, in the precursor fiber sheet after the hot briquetting of above-mentioned molding procedure is processed, the density of above-mentioned carbon chopped fiber is 0.05～0.10g/cm
3, the density of above-mentioned thermosetting resin is 0.10～0.27g/cm
3
2. the manufacture method of porous carbon sheet claimed in claim 1, wherein, above-mentioned molding procedure comprises with a pair of hot plate that is positioned at position parallel to each other carries out the operation that heating and pressurizing is processed.
3. the manufacture method of porous carbon sheet claimed in claim 2, wherein, in above-mentioned molding procedure, the interval body that configures in contact by at least one party with above-mentioned hot plate arranges above-mentioned interval.
4. the manufacture method of porous carbon sheet claimed in claim 2, wherein, in the above-mentioned molding procedure, above-mentioned precursor fiber sheet is sent between the above-mentioned hot plate by phased manner, is transmitting interval, by this hot plate above-mentioned precursor fiber sheet is carried out heating and pressurizing and processes.
5. the manufacture method of porous carbon sheet claimed in claim 1, wherein, above-mentioned molding procedure comprises following operation: with two of above-mentioned precursor fiber sheet surfaces with a pair of state with clamping under, on one side this sheet introduced in the mould with heating unit and slit one side continuously carry out hot briquetting.
6. the manufacture method of porous carbon sheet claimed in claim 5, wherein, the above-mentioned slit of above-mentioned mould is by being arranged by the interval body of pair of metal piece clamping.
7. the manufacture method of porous carbon sheet claimed in claim 5, wherein, above-mentioned a pair of band is at the layer that has the tool oilness with contacted of above-mentioned mould.
8. the manufacture method of porous carbon sheet claimed in claim 5, wherein the above-mentioned slit of above-mentioned mould is with above-mentioned a pair of with contacted the layer with tool oilness.
9. the manufacture method of porous carbon sheet claimed in claim 5, wherein, above-mentioned a pair of band is endless belt.
10. the manufacture method of porous carbon sheet claimed in claim 9, wherein, the two ends contacted of above-mentioned endless belt and above-mentioned mould arrange the tension force transfer part with striding complete cycle.
11. the manufacture method of porous carbon sheet claimed in claim 1 wherein, is supplied with in the above-mentioned precursor fiber sheet of above-mentioned molding procedure, above-mentioned thermosetting resin is 1～3 with respect to the weight ratio of above-mentioned carbon chopped fiber.
12. the manufacture method of porous carbon sheet claimed in claim 1, wherein, the fiber diameter of supplying with the above-mentioned carbon chopped fiber in the above-mentioned precursor fiber sheet of above-mentioned molding procedure is 5～20 μ m.
13. the manufacture method of porous carbon sheet claimed in claim 1, wherein, the above-mentioned precursor fiber sheet of supplying with above-mentioned molding procedure contains the carbonaceous powder.
14. the manufacture method of porous carbon sheet claimed in claim 1, wherein, in above-mentioned carbonation process, above-mentioned precursor fiber sheet is advanced continuously, in the process furnace that keeps inert atmosphere in this process furnace, with 100～10, the heat-up rate of 000 ℃ of/minute scope is warming up to 1,200 ℃ at least, during burning till above-mentioned precursor fiber sheet by above-mentioned process furnace, above-mentioned thermosetting resin carbonization, the porous carbon sheet that above-mentioned carbonation process obtains after finishing is rolled into web-like.
15. the manufacture method of the described porous carbon sheet of claim 14, wherein, in the above-mentioned process furnace of above-mentioned carbonation process, be provided for making the along its length crooked bending part of advancing in one side of above-mentioned precursor fiber sheet on one side, advance while this precursor fiber sheet contacts with this bending part.
16. the manufacture method of the described porous carbon sheet of claim 15, wherein, the interior temperature of process furnace that is provided with above-mentioned bending part is 400～2,700 ℃.
17. the manufacture method of the described porous carbon sheet of claim 16, wherein, the process furnace that is provided with above-mentioned bending part is the process furnace with 400～800 ℃ of temperature provinces.
18. the manufacture method of the described porous carbon sheet of claim 16, wherein, the process furnace that is provided with above-mentioned bending part is the process furnace with 1,600～2,700 ℃ of temperature provinces.
19. the manufacture method of the described porous carbon sheet of claim 15, wherein, the angle of bend when making the precursor fiber sheet limit curved edges is advanced along its length by above-mentioned bending part is 5～25 °.
20. the manufacture method of the described porous carbon sheet of claim 15, wherein, the two sides contacts with above-mentioned bending part successively in the table of above-mentioned precursor fiber sheet, makes in the table of this precursor fiber sheet the two sides crooked.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP283731/2005 | 2005-09-29 | ||
| JP2005283731 | 2005-09-29 | ||
| PCT/JP2006/316708 WO2007037084A1 (en) | 2005-09-29 | 2006-08-25 | Porous carbon sheet and process for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101277912A CN101277912A (en) | 2008-10-01 |
| CN101277912B true CN101277912B (en) | 2013-03-27 |
Family
ID=37899517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800359501A Active CN101277912B (en) | 2005-09-29 | 2006-08-25 | Porous carbon sheet and process for production thereof |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US8142883B2 (en) |
| EP (1) | EP1939156B1 (en) |
| JP (1) | JP5364976B2 (en) |
| KR (2) | KR101302303B1 (en) |
| CN (1) | CN101277912B (en) |
| CA (1) | CA2623129C (en) |
| WO (1) | WO2007037084A1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5311538B2 (en) * | 2008-02-18 | 2013-10-09 | 三菱レイヨン株式会社 | Method for producing porous carbon electrode substrate |
| JP5297701B2 (en) * | 2008-06-20 | 2013-09-25 | 三菱レイヨン株式会社 | Method for producing electrode substrate for polymer electrolyte fuel cell |
| US8088697B2 (en) * | 2008-09-18 | 2012-01-03 | Fuelcell Energy, Inc. | Fibrous ceramic material and method for making the same |
| GB0902312D0 (en) * | 2009-02-12 | 2009-04-01 | Johnson Matthey Plc | Gas diffusion substrate |
| JP5448608B2 (en) * | 2009-06-29 | 2014-03-19 | 三菱レイヨン株式会社 | Continuous production method of porous carbon electrode substrate with less undulation and warpage |
| JP5728802B2 (en) * | 2009-09-18 | 2015-06-03 | 三菱レイヨン株式会社 | Porous carbon electrode substrate and method for producing the same |
| JP5713003B2 (en) | 2011-01-21 | 2015-05-07 | 三菱レイヨン株式会社 | Porous electrode substrate, production method thereof, membrane-electrode assembly, polymer electrolyte fuel cell, precursor sheet, and fibrillar fiber |
| CA2825663C (en) | 2011-01-27 | 2023-03-21 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for manufacturing same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
| CN102698713B (en) * | 2012-05-24 | 2014-05-21 | 山东中烟工业有限责任公司 | Porous carbon piece, preparation method of porous carbon piece, and application of porous carbon piece in cigarette filter |
| CN104583763B (en) | 2012-06-25 | 2017-03-08 | 3M创新有限公司 | Sensor element and its preparation and application |
| KR101468866B1 (en) * | 2012-07-17 | 2014-12-04 | 한국에너지기술연구원 | Method for preparing carbon paper for fuel cell, the carbon paper prepared using the method and fuel cell comprising the carbon paper |
| JP6048105B2 (en) * | 2012-12-12 | 2016-12-21 | 住友電気工業株式会社 | Optical fiber manufacturing method and optical fiber |
| KR101392227B1 (en) * | 2013-03-21 | 2014-05-27 | 한국에너지기술연구원 | Carbon fiber web comprising polymer nanofiber |
| JP6489010B2 (en) | 2014-02-26 | 2019-03-27 | 東レ株式会社 | Porous carbon material, carbon material reinforced composite material, porous carbon material precursor, method for producing porous carbon material precursor, and method for producing porous carbon material |
| JP6287641B2 (en) * | 2014-07-01 | 2018-03-07 | トヨタ紡織株式会社 | Non-woven fabric making method and non-woven fabric making device |
| EP3208874B1 (en) | 2014-10-17 | 2020-03-18 | Toray Industries, Inc. | Carbon sheet, gas diffusion electrode base material, and fuel cell |
| EP3217456B1 (en) * | 2014-11-04 | 2020-05-06 | Mitsubishi Chemical Corporation | Porous electrode substrate, membrane/electrode assembly using same, and solid polymer fuel cell using same |
| WO2016193992A1 (en) * | 2015-05-29 | 2016-12-08 | Ambuja Intermediates Ltd | A novel and environment friendly "zero solid discharge" treatment used in dyes and dyes intermediate industries |
| KR102630169B1 (en) * | 2015-12-11 | 2024-01-29 | 도레이 카부시키가이샤 | Carbon sheets, gas diffusion electrode substrates, and fuel cells |
| CN108432007B (en) | 2015-12-24 | 2021-03-02 | 东丽株式会社 | Gas diffusion electrode |
| WO2017110692A1 (en) | 2015-12-24 | 2017-06-29 | 東レ株式会社 | Gas diffusion electrode and fuel cell |
| US10790516B2 (en) | 2015-12-24 | 2020-09-29 | Toray Industries, Inc. | Gas diffusion electrode and method for manufacturing same |
| KR102579111B1 (en) * | 2016-06-02 | 2023-09-15 | 이승수 | Heating unit manufacturing method and beauty equipment having the same |
| JP7310127B2 (en) * | 2018-12-14 | 2023-07-19 | 東レ株式会社 | Porous carbon electrode substrate and manufacturing method thereof |
| WO2020226620A1 (en) * | 2019-05-06 | 2020-11-12 | Michael Kwabena Opoku | Method of making nanomaterials from a renewable carbon source |
| WO2020235638A1 (en) * | 2019-05-23 | 2020-11-26 | 国立研究開発法人物質・材料研究機構 | Porous carbon structure, manufacturing method therefor, positive electrode material using same, and battery using same |
| TWI742804B (en) * | 2019-08-21 | 2021-10-11 | 日商日本製紙股份有限公司 | Activated carbon fiber sheet for motor vehicle canister |
| KR102296603B1 (en) * | 2020-10-26 | 2021-09-01 | 한영산업주식회사 | Method of manufacturing heat melted non-woven fabric with excellent strength and elongation |
| CN115249817B (en) * | 2021-04-28 | 2024-01-19 | 华南理工大学 | Catalytic graphitization method of carbon paper material for fuel cell gas diffusion layer |
| CN113878835B (en) * | 2021-12-08 | 2022-03-08 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1139471A1 (en) * | 1999-09-22 | 2001-10-04 | Toray Industries, Inc. | Porous, electrically conductive sheet and method for production thereof |
| CN1762885A (en) * | 2005-08-05 | 2006-04-26 | 阳东县有源树酯纤维科技有限公司 | Composite resin plate |
| EP1539470B1 (en) * | 2002-03-07 | 2007-04-18 | Ulrich Haupt | Pressing device for a double-band press |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57166354A (en) * | 1981-04-01 | 1982-10-13 | Kureha Chemical Ind Co Ltd | Porous carbon formed body and manufacture |
| US4670300A (en) * | 1985-07-03 | 1987-06-02 | International Fuel Cells Corporation | Carbon-graphite component for an electrochemical cell and method for making the component |
| US4985316A (en) * | 1988-02-12 | 1991-01-15 | International Fuel Cells Corporation | Corrosion resistant fuel cell substrates |
| US5578255A (en) * | 1989-10-26 | 1996-11-26 | Mitsubishi Chemical Corporation | Method of making carbon fiber reinforced carbon composites |
| EP0651452A1 (en) * | 1993-11-01 | 1995-05-03 | Osaka Gas Co., Ltd. | Porous carbonaceous material and a method for producing the same |
| JP4051714B2 (en) | 1995-12-06 | 2008-02-27 | 東レ株式会社 | Electrode substrate for polymer electrolyte fuel cell and method for producing the same |
| JPH10291869A (en) * | 1997-04-22 | 1998-11-04 | Unitika Ltd | Carbon heat insulating material and its production |
| US6182171B1 (en) * | 1997-06-06 | 2001-01-30 | Nissan Motor Co., Ltd. | Information communication system and method applicable to in-vehicle networking architecture |
| JP3888057B2 (en) * | 1998-05-27 | 2007-02-28 | 東レ株式会社 | Carbon fiber paper for polymer electrolyte fuel cells |
| KR20010112912A (en) | 2000-01-27 | 2001-12-22 | 나가이 야타로 | Porous Carbon Electrode Substrate and Its Production Method and Carbon Fiber Paper |
| EP1302293B1 (en) * | 2000-07-14 | 2007-11-14 | Mitsubishi Rayon Co., Ltd. | Process for producing carbonaceous material sheet |
| US7144476B2 (en) | 2002-04-12 | 2006-12-05 | Sgl Carbon Ag | Carbon fiber electrode substrate for electrochemical cells |
| JP2004256959A (en) * | 2003-02-27 | 2004-09-16 | Toray Ind Inc | Method and apparatus for producing sheet-like base material |
| US7410719B2 (en) * | 2003-03-26 | 2008-08-12 | Toray Industries, Inc. | Porous carbon base material, method for preparation thereof, gas-diffusing material film-electrode jointed article, and fuel cell |
| JP5055682B2 (en) | 2003-03-27 | 2012-10-24 | 東レ株式会社 | Porous carbon plate and method for producing the same |
| JP2006264329A (en) * | 2005-02-28 | 2006-10-05 | Toray Ind Inc | Fiber-reinforced plastic long sheet and its manufacturing method |
-
2006
- 2006-08-25 WO PCT/JP2006/316708 patent/WO2007037084A1/en active Application Filing
- 2006-08-25 KR KR1020087007733A patent/KR101302303B1/en active IP Right Grant
- 2006-08-25 KR KR1020137013753A patent/KR101320730B1/en active IP Right Grant
- 2006-08-25 JP JP2006529344A patent/JP5364976B2/en active Active
- 2006-08-25 EP EP06796781A patent/EP1939156B1/en active Active
- 2006-08-25 CN CN2006800359501A patent/CN101277912B/en active Active
- 2006-08-25 US US12/066,875 patent/US8142883B2/en active Active
- 2006-08-25 CA CA2623129A patent/CA2623129C/en active Active
-
2012
- 2012-02-21 US US13/401,739 patent/US8641939B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1139471A1 (en) * | 1999-09-22 | 2001-10-04 | Toray Industries, Inc. | Porous, electrically conductive sheet and method for production thereof |
| EP1539470B1 (en) * | 2002-03-07 | 2007-04-18 | Ulrich Haupt | Pressing device for a double-band press |
| CN1762885A (en) * | 2005-08-05 | 2006-04-26 | 阳东县有源树酯纤维科技有限公司 | Composite resin plate |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2004-256959A 2004.09.16 |
| JP特开平10-291869A 1998.11.04 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1939156B1 (en) | 2012-08-15 |
| CA2623129A1 (en) | 2007-04-05 |
| KR20130065734A (en) | 2013-06-19 |
| WO2007037084A1 (en) | 2007-04-05 |
| US20090258206A1 (en) | 2009-10-15 |
| CA2623129C (en) | 2013-07-02 |
| CN101277912A (en) | 2008-10-01 |
| US8142883B2 (en) | 2012-03-27 |
| JP5364976B2 (en) | 2013-12-11 |
| US8641939B2 (en) | 2014-02-04 |
| KR20080060233A (en) | 2008-07-01 |
| US20120153522A1 (en) | 2012-06-21 |
| KR101320730B1 (en) | 2013-10-21 |
| EP1939156A4 (en) | 2010-11-10 |
| JPWO2007037084A1 (en) | 2009-04-02 |
| EP1939156A1 (en) | 2008-07-02 |
| KR101302303B1 (en) | 2013-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101277912B (en) | Porous carbon sheet and process for production thereof | |
| US7959750B2 (en) | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet | |
| KR101294825B1 (en) | Method for preparing carbon substrate for gas diffusion layer of polymer electrolyte membrane fuel cell, carbon substrate prepared thereby, and system for manufacturing the same | |
| KR101094566B1 (en) | Porous Carbon Base Material, Gas-Diffusing Material, Film-Electrode Jointed Article, and Fuel Cell | |
| KR101324703B1 (en) | Method for preparing carbon substrate comprising activated carbon fiber, carbon substrate prepared thereby | |
| JP2020133006A (en) | Method for producing carbon fiber sheet | |
| JP2007002394A (en) | Carbon fiber sheet, method for producing the same and heat treatment furnace for sheet-like material | |
| JP4345538B2 (en) | Method for producing carbon fiber sheet | |
| KR101090601B1 (en) | Gas diffusion layer carbon substrate of Polymer Electrolyte Membrane type fuel cell and its manufacturing method, its manufacturing system | |
| JP4728528B2 (en) | Thermosetting device and thermosetting method for porous carbon-based molded product precursor sheet | |
| JP2006264329A (en) | Fiber-reinforced plastic long sheet and its manufacturing method | |
| JP4661152B2 (en) | Method and apparatus for manufacturing molded product | |
| JP6458589B2 (en) | Sheet material, integrated molded product, and integrated molded product manufacturing method | |
| JP6181308B2 (en) | Dry fuel cell precursor substrate and substrate manufacturing method | |
| JPH10302831A (en) | Manufacture of sodium sulfur battery anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |